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SOLAR PHOTOCHEMICAL TECHNOLOGY 

FOR POTABLE WATER TREATMENT: 
DISINFECTION AND DETOXIFICATION 






By 

ADRIENNE TERESA COOPER 












A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL 

OF THE UNP7ERSITY OF FLORIDA IN PARTIAL FULFILLMENT 

OF THE REQUIREMENTS FOR THE DEGREE OF 

DOCTOR OF PHILOSOPHY 

UNIVERSITY OF FLORIDA 

1998 






Copyright 1998 
Adrienne Teresa Cooper 



This dissertation is dedicated to my grandmothers, Gewenith 
Manning and the late Ethel Cummings, who were women for their time 
and to my nephew Fatin D. Cooper who is the future. 



ACKNOWLEDGMENTS 

The research conducted for this dissertation was supported by the 
National Science Foundation through the University of Florida College of 
Engineering Minority Engineering Doctoral Initiative. 

Appreciation is expressed to my committee chairman Dr. Thomas 
Crisman and cochairman Dr. D. Y. Goswami for their sage advice and 
unwavering support over the last few years. Acknowledgment and 
gratitude are extended to committee member Dr. Michael Annable for his 
support and generous provision of access to analytical equipment and 
laboratory facilities; to committee member Dr. Seymour S. Block whose 
knowledge of disinfection has served as a valuable resource and who 
graciously allowed me the use of his laboratory; committee member Dr. 
Paul Chadik, who helped to steer me in the right direction from the very 
beginning; to Sanjay Puranik for sharing his knowledge of analytical 
chemistry; to Chuck Garretson for making available his wealth of 
mechanical capabilities, keen insight and ever present smile; to Michael 
McCaskill and Michael Oliver for their diligent assistance in the 
laboratory; and to Barbara Walker and Berdenia Monroe for their 
administrative support and friendship. My gratitude and thanks are due to 
committee member Dr. Jonathan Earle for his guidance, encouragement, 
confidence and that extra push when I needed it. 



IV 



The insight, support and friendship of my colleagues in the Solar 
Energy Group, the Center for Wetlands and Environmental Engineering 
Sciences have truly enriched my learning experience here at the University 
of Florida, and they, in their own ways, have contributed to the achievement 
of this goal. 

A special thank you is extended to the entire Earle family, Celia, 
Jeremy, Kevin and Mrs. Yvonne Earle, for being my "Gainesville Family." 
My parents Dr. and Mrs. Trenton Cooper, my sister Mrs. Edris 
Anifowoshe, and my nephew, Fatin Cooper, have provided invaluable 
support in every way imaginable. I want to convey a loving thank you to my 
special friend, Abdoulaye Kaba, for his support during the writing of this 
dissertation. Others have provided valuable support, insight, friendship 
and shoulders over the last years including Sonja Jonas, Clayton Clark, the 
Makaveli Gainesville Tennis Crew, and the Black Graduate Student 
Organization. 

Finally and most importantly, I would like to give praise to the 
Creator for making it all possible. 



TABLE OF CONTENTS 

page 

ACKNOWLEDGMENTS iv 

LIST OF TABLES ix 

LIST OF FIGURES xii 

KEY TO SYMBOLS xviii 

ABSTRACT xix 

CHAPTERS 

1 INTRODUCTION 1 

Research Significance 1 

Theory of Photochemical Water Treatment 4 

Photocatalysis 5 

Photosensitization 8 

The Solar Resource 10 

Research Objectives 12 

2 REVIEW OF SOLAR BASED WATER TREATMENT 14 

Physical Processes 15 

Distillation Processes 15 

Passive distillation 15 

Active distillation 21 

Pasteurization Processes 24 

Photo Processes 27 

Solar Disinfection 28 

SODIS 28 

Halosol 29 

Photocatalysis 29 

Photosensitization 30 

Summary 32 



VI 



3 EXPERIMENTAL DESIGN AND METHODS 34 

Choice of Experimental Parameters 34 

Contaminants 35 

Catalyst Choice 35 

Choice of Photosensitizer 37 

Reactor Design 39 

pH 43 

Catalyst/Sensitizer Concentration 44 

Laboratory Experimental Design 45 

Materials and Methods 46 

Reaction Vessels 46 

Bacterial Inoculation 47 

Reactor Chamber 49 

Photocatalysis Reactor Setup 49 

Photocatalysis Sampling and Analysis 50 

Photosensitization Reactor Setup 51 

Photosensitization Sampling and Analysis 52 

Combination Experimental Setup, Sampling and Analysis 52 

Experiments for Confirmation of Previous Work with Bromacil 53 

4 RESULTS AND DISCUSSION 54 

Dye Photosensitization 54 

General Comments About Experimental Data 56 

Statistical Treatment of the Data 58 

Presentation of Results and Identification of General Trends 62 

Data Analysis by ANOM 81 

Effect of Sunlight 82 

Effect of pH 86 

Effect of Dye Concentration 89 

Effect of Initial Coliform Density 97 

Reactor Efficacy 99 

Summary 101 

Photocatalysis with Titanium Dioxide 102 

General Comments About Experimental Data 104 

Statistical Treatment of the Data 105 

Presentation of Results and Identification of General Trends 105 

Data Analysis by ANOM 112 

Effect of Light 113 

Effect of pH 117 

Effect of Ti0 2 Concentration 120 

Multiple Parameter Effects 128 

Effect of Initial Colony Density on Disinfection 129 

Other Effects 131 

Photocatalysis vs. Air Stripping 132 

Summary 134 

Ti0 2 Photocatalysis Combined With Methylene Blue 135 

General Comments About Experimental Data 136 



vn 



Statistical Treatment of the Data 137 

Disinfection 137 

Detoxification 142 

Summary 152 

Kinetic Considerations 152 

Detoxification 152 

Disinfection 154 

General Summary of Results 157 

5 SUMMARY AND CONCLUSIONS 159 

Summary 159 

Process Efficacy Comparison for Simultaneous Treatment 159 

Drinking Water Quality 160 

Conclusions 160 

Recommendations for Future Work 161 

REFERENCES 163 

APPENDICES 

A EXPERIMENTAL DATA 176 

B LIGHT MEASUREMENT 260 

BIOGRAPHICAL SKETCH 269 






vm 



LIST OF TABLES 

Table page 

1-1. Spectral Distribution of Solar Radiation 11 

2-1. Examples of Photocatalytic Treatment of Water and Wastewater .... 30 

2-2. Examples of Photocatalytic Treatment of Water and Wastewater .... 31 

2-3. Summary of Photosensitized Treatment of Water and Wastewater. . 32 

3-1. Photostability of Semiconductor Oxides Tested by Carey and Oliver 

(1980) 37 

3-2. Order of Effectiveness of Dyes at 10" 4 M Concentration on E. Coli 

After 24 Hours Exposure to Light at Room Temperature 40 

3-3. Design for Ti0 2 Photocatalytic Lab Experiments 46 

3-4. Design for Photosensitization Lab Experiments 46 

3-5. Design for Combination Lab Experiments 46 

4-1. Insolation Measurements from Dye Sensitization Experiments 55 

4-2. Descriptive Statistics of Measured Data for all Experiments 56 

4-3. Average Standard Deviations for all Dye Photosensitization 

Experiments 57 

4-4. Mean Fractional Survival (± 31%) of E. coli @ t= 30 minutes in MB 

Experiments 59 

4-5. Mean Fractional Survival (±25%) of E. coli in MB Experiments 65 

4-6. Mean Fractional Survival (±13%) of E. coli in RB Experiments 68 

4-7. Benzene (±51) and Toluene (±29) Concentrations (ppb) in MB 

Experiments 70 

4-8. Benzene (± 46) and Toluene (± 36) Concentrations (ppb) in RB 

Experiments 70 



IX 



4-9. Normalized Benzene (±0.09) and Toluene (± 0.11) Concentration in 

MB Experiments 76 

4-10. Normalized Benzene (±0.06) and Toluene (±0.07) Concentration in RB 
Experiments 77 

4-11. Calculated ANOM Values for Dye Photosensitized Disinfection 82 

4-12. Sunlight Subgroup Averages for Dye Photosensitized Disinfection; 

Values are Fractional Survival of E. coli 83 

4-13. pH Subgroup Averages for Dye Photosensitized Disinfection. Values 
are Fractional Survival of E. coli 86 

4-14. Dye Concentration Subgroup Averages in Disinfection Experiments. 
Values are Fractional Survival of E. Coli 90 

4-15. Mean Fractional Survival of Bacteria in Ti0 2 Experiments 107 

4-16. Mean Concentration of BTEX (ppb) in Ti0 2 Experiments 108 

4-17. Calculated ANOM Values for Ti0 2 Photocatalysis 113 

4-18. UV Light Subgroup Averages for Ti0 2 Photocatalysis. Values are 
Fractional Survival of Bacteria and Normalized Chemical 
Concentration 114 

4-19. pH Subgroup Averages for Ti0 2 Photocatalysis. Values are 
Fractional Survival of Bacteria and Normalized Chemical 
Concentration 117 

4-20. Ti0 2 Concentration Subgroup Averages for Disinfection. Values are 
Fractional Survival of Bacteria and Normalized Chemical 
Concentration 121 

4-21. Mean Values for Fractional Survival as a Function of Light, pH and 
Ti0 2 Concentration at t=240 Minutes 128 



2 



4-22. Mean Normalized Benzene Concentration After 30 Minutes in TiO 

Experiments 129 

4-23. Descriptive Statistics for Initial Colony Density in Ti0 2 Experiments 130 

4-24. Vapor Pressure Values for BTEX components 133 

4-25. Measured Sunlight Intensity in Combination Experiments 136 

4-26. Average Standard Deviations for all Combination Experiments 137 

4-27. Mean Fractional Survival (±14.1%) of E. Coli in Combination 

Experiments 139 



4-28. Calculated ANOM Values for Combination Experiments 139 

4-29. Sunlight Subgroup Averages for Combined Experiments. Values are 
Fractional Survival of Bacteria and Normalized Chemical 
Concentration 139 

4-30. Photochemical Subgroup Averages for Combination Experiments; 
Values are Fractional Survival of E. coli and Normalized 
Chemical Concentration 140 

4-31. Mean Concentration (ppb) of Benzene (±120) and Toluene (±199) in 
Combination Experiments; Lf t A = 433-833 W/m 2 , I m A = 25-40 
W/m 2 147 



4-32. Experimental First - Order Rate Constants (min "') for TiO 



2 



Photocatalytic Experiments 153 

4-33. Correlation Statistics for Least Squares Linear Regression of Kinetic 
Data; Confidence Level is 95% 154 

4-34. First Order Rate Constants for All Photochemical Disinfection 

Experiments 157 

4-35. Time to Complete Destruction by Photochemical Treatment 158 



XI 



LIST OF FIGURES 

Fi gure page 

1-1. Graphical Representation of the Generation of e - /h + Pairs and 
Recombination by Photocatalytic Reaction on the Surface of 
aSemiconductor Particle 7 

2-1. Conventional Passive Solar Basin Still 17 

2-2. Schematic of Flash Distillation Using Solar Collector 22 

3-1. Ti0 2 Reaction Vessel 47 

3-2. Photosensitization Reaction Vessel 48 

3-3. Graphical Representation of Bacterial Inoculation 48 

3-4. Ultraviolet Light and Dark Reactor Chamber 50 



4-1. MB Destruction of E. coli in Sunlight; (a) pH =10, I av = 542-696 W/m 



2 



avg 



(b) pH =7, I = 665-891 W/m 2 63 



avg 



4-2. Destruction of E. coli in sunlight with 1 mg/L MB; (a) pH =10, I = 



542-696 W/m 2 and (b) pH 7, T = 665-891 W/m 2 64 



avg 



4-3. RB Destruction of E. coli in Sunlight; (a) pH = 7, T = 746-856 W/m 



2 



avg 



(b) pH = 10, 1 = 715-775 W/m 2 67 



avg 



4-4. RB Destruction of E. coli at pH =7, 1 = 715-775 W/m 2 ; (a) 5 mg/L RB 
and (b) 10 mg/L RB 68 

4-5. Benzene Concentration as a Function of Time and MB Concentration 
in Sunlight; (a) pH=10, T = 542-696 W/m 2 (b) pH=7, T = 665-891 
W/m 2 g 72 

4-6. Toluene Concentration as a Function of Time and MB Concentration 
in Sunlight; (a) pH =10, T = 542-696 W/m 2 (b) pH=7, 1 = 665-891 
W/m 2 .* 73 

4-7. Benzene Concentration as a Function of Time and RB Concentration 
in Sunlight; (a) pH =10, T = 715-775 W/m 2 (b) pH=7, T = 746-856 
W/m 2 Z 74 



xn 



4-8. Toluene Concentration as a Function of Time and RB Concentration 
in Sunlight; (a) pH =10, I ave = 715-775 W/m 2 (b) pH=7, I ave = 746-856 
W/m 2 75 

4-9. Normalized Benzene Concentration in Sunlight with 0.1 mg/L MB, 

(a) pH =10, I avg = 542-696 W/m 2 (b) pH=7, I avg = 665-891 W/m 2 78 

4-10. Normalized Toluene Concentration in Sunlight with 0.1 mg/L MB; 

(a) pH =10, I avg = 542-696 W/m 2 (b) pH=7, I avg = 665-891 W/m 2 79 

4-11. Normalized Benzene Concentration in Sunlight with 0.1 mg/L RB, (a) 
pH =10, I avg = 715-775 W/m 2 (b) pH=7, I avg = 746-856 W/m 2 80 

4-12. Normalized Toluene Concentration in Sunlight with 0.1 mg/L RB, (a) 
pH =10, I avg = 715-775 W/m 2 (b) pH=7, I avg = 746-856 W/m 2 81 

4-13. Significance of Sunlight, Based on ANOM, in MB Experiments (a) 5 
Minutes (b) 15 Minutes (c) 30 Minutes 84 

4-14. Significance of Sunlight, Based on ANOM, in RB Experiments; (a) 5 
Minutes (b) 15 Mintues (c) 30 Minutes 85 

4-15. Significance of pH, Based on ANOM, in MB Experiments; (a) 5 

Minutes (b) 15 Minutes (c) 30 Minutes 87 

4-16. Significance of pH, Based on ANOM, in RB Experiments; (a) 5 

Mintues (b) 15 Minutes (c) 30 Minutes 88 

4-17. Statistical Significance of MB Concentration, Based on ANOM, on 
Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30 
Minutes 91 

4-18. Statistical Significance of RB Concentration, Based on ANOM, on 
Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30 
Minutes 92 

4-19. Comparison of Disinfection Efficacy of Control and 0.1 mg/ L MB in 

Sunlight at 5 minutes, Based on ANOM 93 

4-20. Comparison of Disinfection Efficacy of Control and 1 mg/L MB in 

Sunlight at 5 minutes, Based on ANOM 94 

4-21. Comparison of Disinfection Efficacy of Control and 5 mg/L MB in 

Sunlight at 5 minutes, Based on ANOM 94 

4-22. Comparison of Disinfection Efficacy of Control and 10 mg/L MB in 

Sunlight at 5 minutes, Based on ANOM 95 

4-23. Comparison of Disinfection Efficacy of 0.1 mg/ L and 10 mg/L MB in 
Sunlight at 5 minutes, Based on ANOM 95 



xm 



4-24. Comparison of Disinfection Efficacy of 1 rag/ L and 10 mg/L MB in 

Sunlight at 5 minutes, Based on ANOM 96 

4-25. Comparison of Disinfection Efficacy of 5 mg/ L and 10 mg/L MB in 

Sunlight at 5 minutes, Based on ANOM 96 

4-26. Fractional Survival of E. coli in sunlight at t=30 minutes as a 

Function of MB Concentration; Bars are One Standard Deviation 
97 

4-27. Least Squares Regression of Natural Logarithm of Fractional 
Survival of E. coli as a Function of MB Concentration at t=5 
Minutes 98 

4-28. Initial Colony Count vs. Fractional Survival of E. coli at t=60 Minutes 
for MB Experiments 98 

4-29. Initial Colony Count vs. Fractional Survival of E. coli at t=30 Minutes 
in RB Experiments 99 

4-30. Ti0 2 Photocatalytic Disinfection in UV Light (29 W/m 2 ); Error Bars 

are One Standard Deviation; (a) pH = 4 (b) pH = 7 106 

4-31. Destruction of Benzene in Reactors 3 and 4 as a Function of Time; 
Reactors Contained 0.01% Ti0 2 and were Irradiated for 60 
minutes under UV Lamps (29 W/m 2 ) 110 

4-32. Benzene Concentration in UV Light (29 W/m 2 ) as a Function of Time 
and Ti0 2 Concentration; Error Bars are One Standard Deviation, 
(a) pH =4, (b) pH = 7 110 

4-33. Toluene Concentration in UV Light (29 W/m 2 ) as a Function of Time 
and Ti0 2 Concentration; Error Bars are One Standard Deviation, 
(a) pH =4, (b) pH = 7 Ill 

4-34. m&p Xylene Concentration in UV Light (29 W/m 2 ) as a Function of 
Time and Ti0 2 Concentration; Error Bars are One Standard 
Deviation, (a) pH =4, (b) pH = 7 112 

4-35. Significance of UV Light (29 W/m 2 ), Based on ANOM, on Bacteria in 
Ti0 2 Experiments at 120 Minutes 115 

4-36. Significance of UV Light (29 W/m 2 ), Based on ANOM, on Benzene in 
Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 115 

4-37. Significance of UV Light (29 W/m 2 ), Based on ANOM, on Toluene in 
Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 116 

4-38. Effect of UV Light (29 W/m 2 ) on Fractional Survival of Bacteria in All 

Reactors in Ti0 2 Experiments; Bars are One Standard Deviationll6 



xiv 



4-39. Significance of pH, Based on ANOM, to Bacteria Destruction in Ti0 2 
Experiments at 120 Minutes 118 

4-40. Significance of pH, Based on ANOM, to Benzene Destruction in Ti0 2 
Experiments (a) 30 Minutes (b) 60 Minutes 119 

4-41. Significance of pH, Based on ANOM, to Toluene Destruction in Ti0 2 
Experiments (a) 30 Minutes (b) 60 Minutes 120 

4-42. Significance of Ti0 2 Concentration, Based on ANOM, on Bacteria in 
Photocatalysis Experiments at 120 Minutes 121 

4-43. Significance of Ti0 2 Concentration, Based on ANOM, on Benzene in 
Photocatalysis Experiments; (a) 30 Minutes (b) 60 Minutes 122 

4-44. Significance of Ti0 2 Concentration, Based on ANOM, on Toluene in 
Photocatalysis Experiments; (a) 30 Minutes (b) 60 Minutes 123 

4-45. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic Disinfection 
at 120 Minutes, Based on ANOM 124 

4-46. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic Disinfection 
at 120 Minutes, Based on ANOM 124 

4-47. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic Disinfection 
at 120 Minutes, Based on ANOM 125 

4-48. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic Disinfection at 
120 Minutes, Based on ANOM 125 

4-49. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic Destruction of 
Benzene at 60 Minutes, Based on ANOM 126 

4-50. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic Destruction of 
Benzene at 60 Minutes, Based on ANOM 126 

4-51. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic Destruction of 
Benzene at 60 Minutes, Based on ANOM 127 

4-52. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic Destruction of 
Benzene at 60 Minutes, Based on ANOM 127 

4-53. Fractional Survival of Bacteria as a Function of UV Light (29 W/m 2 ) 
and pH in Ti0 2 Experiments; Bars are One Standard Deviation 
130 

4-54. Effect of UV Light (29 W/m 2 ) and pH on the Destruction of Benzene in 
Ti0 2 Experiments; Bars are One Standard Deviation 130 

4-55. Initial Colony Count vs. Fractional Survival of Bacteria at t=120 

Minutes for Ti0 2 Photocatalysis 131 



xv 






4-56. Normalized Concentrations of BTEX Components in pH 7 Dark 

Experiments with 0.01% Ti0 2 133 

4-57. Normalized Concentrations of BTEX Components in pH 4 Dark 

Experiments with 0.01% Ti0 2 134 

4-58. Destruction of E. coli in Sunlight (I T()t Avg = 433-853 W/m 2 , I w Avg = 25-40 
W/m 2 ) in Combination Experiments 138 

4-59. Significance of Sunlight (I Tot Avg = 433-853 W/m 2 , I uv _ Avg = 25-40 W/m 2 ) 
on E. coli Destruction, Based on ANOM, in Combination 
Experiments; (a) 5 Minutes (b) 15 Minutes (c) 30 Minutes 141 

4-60. Significance of Photochemical on E. coli Destruction, Based on 
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15 
Minutes (c) 30 Minutes 143 

4-61. Significance of Ti0 2 vs MB on E. coli Destruction, Based on ANOM, in 
Combination Experiments; (a) 5 Minutes (b) 15 Miiues (c) 30 
Minutes 144 

4-62. Significance of Ti0 2 vs Both on E. coli Destruction, Based on ANOM, 
in Combination Experiment; (a) 5 Minutes (b) 15 Minutes (c) 30 
Minutes 145 

4-63. Significance of MB vs Both on E. coli Destruction, Based on ANOM, 
in Combination Experiments; (a) 5 Minutes (b) 15 Minutes (c) 30 
Minutes 146 

4-64. Normalized Concentration as a Function of Time in Combination 
Experiments. L^ Avg = 433-833 W/m 2 , I uv Avg = 25-40 W/m 2 ; (a) 
Benzene (b) Toluene 147 

4-65. Significance of Photochemical on Benzene Destruction, Based on 
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 148 

4-66. Significance of Photochemical on Toluene Destruction, Based on 
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 149 

4-67. Significance of Ti0 2 vs Both on Benzene Destruction, Based on 
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 150 

4-68. Significance of Ti0 2 vs Both on Toluene Destruction, Based on 
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 151 



xvi 



4-69. Least Squares Linear Regression of First Order Rate Equation for 

Disinfection in UV Light (29 W/m 2 ) with 0.05% Ti0 2 and pH = 4; r 2 
= 0.90, p-value = 0.0025 155 

4-70. Least Squares Linear Regression of First Order Rate Equation for 

Disinfection in UV Light (29 W/m 2 ) with 0.10% Ti0 2 and pH = 7; r 2 
= 0.55, p-value = 0.019 155 

4-71. Least Squares Linear Regression of First Order Rate Equation for 
Disinfection in Sunlight (715-775 W/m 2 ) with no photochemical 
and pH = 10; r 2 = 0.99, p-value = 0.0001 156 

4-72. Least Squares Linear Regression of First Order Rate Equation for 

Disinfection in Sunlight (746-856 W/m 2 ) with 1 mg/L RB and pH = 
7; r 2 = 0.95, p-value = 0.0003 156 



xvn 



KEY TO SYMBOLS 

\ Wavelength, nm 

h Planck's constant, 6.625 x 10 J4 Js 

c Speed of light, 3.0 x 10 10 cm/s 

e Band gap energy, ev 

hv Li g ht energy 

n + Positive hole in the valence band 

e - Electron 

iX* Excited singlet state of component X 

3x* Excited triplet state of component X 

X* Excited state of component X 

! X Singlet state of component X 

3x Triplet state of component X 

R Hydrocarbon group 

I sc Solar constant 

C t Concentration at time, t 

N t Colony density at time, t 

I Insolation, W/m 2 

s Standard Deviation 

X Grand Average of all Data in ANOM 

X Subgroup Average for ANOM 

s Average standard deviation 

r Average Range 

H ANOM Critical Value 

v degrees of freedom 

d 2 2 bias correction factor for ANOM 

a significance factor 



xvin 



Abstract of Dissertation Presented to the Graduate School 

of the University of Florida in Partial Fulfillment of the 

Requirements for the Degree of Doctor of Philosophy 

SOLAR PHOTOCHEMICAL TECHNOLOGY 

FOR POTABLE WATER TREATMENT: 
DISINFECTION AND DETOXIFICATION 

By 

Adrienne Teresa Cooper 
August 1998 

Chairperson: Thomas Crisman 

Cochairperson: D. Yogi Goswami 

Major Department: Environmental Engineering Sciences 

Clean water is scarce in many countries, and the goal of universal 
access to water and sanitation has not yet been achieved. Standard water 
treatment techniques are often expensive both in capital investment and 
operation and maintenance, particularly in lesser developed communities 
where resources are scarce. 

Solar photochemistry has shown promise as an appropriate 
alternative technology for treatment of water, and provides potential for 
simultaneous disinfection and destruction of organic chemicals. The need 
for simultaneous treatment arises when conditions of contamination of 
source water, such as ground water, occurs. Potential sources of 
contamination are industrial and agricultural runoff or leakage of 
underground storage tanks (gasoline) and sewerage lines. 






xix 



In a series of bench scale experiments, three photochemical 
technologies, Ti0 2 photocatalysis, dye photosensitization and a combination 
of dye photosensitization and Ti0 2 photocatalysis, were evaluated for their 
efficacy for simultaneous removal of coliform bacteria and aromatic 
hydrocarbons in drinking water under a variety of pH and photochemical 
concentration conditions. 

Series of 100 ml and 500 ml reactors, containing various 
concentrations of Ti0 2 , and two pH levels (4 and 7), were inoculated with 
mixed bacteria species, benzene, toluene, and xylene, and illuminated 
under ultraviolet light for several hours. Under most conditions both the 
chemical and bacteriological contaminants were destroyed within an hour. 

In photosensitization experiments, the 500 ml reactors were charged 
with several concentrations of rose bengal or methylene blue and neutral, 
pH 7, or basic, pH 10, water. After inoculation with Escherichia coli, 
benzene and toluene, the reactors were illuminated for four hours in 
sunlight. In all cases, the water was disinfected within one hour; however, 
destruction of the chemical contaminants did not occur. 

The 500 ml hybrid reactors, loaded with 0.01% Ti0 2 and/or 5 mg/L 
methylene blue, were also illuminated in sunlight. The inoculations of 
Escherichia coli, benzene, and toluene were completely destroyed after two 
hours in all of the reactors which contained Ti0 2 ; however, the presence of 
methylene blue inhibited the reaction. 



xx 



CHAPTER 1 
INTRODUCTION 

Research Significance 

Clean and safe water is a requirement for healthy living and 
development. While concerns with most water related diseases have been 
virtually eliminated in most developed regions, such as Western Europe 
and North America, diseases related to either the quantity or quality of 
water supply are still a major problem in other parts of the world 

In 1977 Stein reported that 25,000 deaths occurred daily from water 
borne diseases. In an effort to reduce these deaths, the United Nations 
declared the ten year period from 1981 to 1990 the International Drinking 
Water Supply and Sanitation Decade. The goal of the decade was to provide 
universal access to safe water and sanitation. While many advances were 
made during this period to increase the supply of safe drinking water for 
the global human population, universal access has yet to be achieved. 
According to World Health Organization (WHO) estimates, as of 1990, 18% 
of urban populations and 36% of rural populations (approximately 1.23 
billion people) are still without access to safe drinking water supplies 
(Christmas 1990). An inexpensive supply of clean water is one of the most 
pressing public health issues facing developing communities. 

Over 10 million deaths result from more than 250 million new cases 
of water borne diseases yearly (Hazen and Toranzos 1990). During 1993 



there were 272,500 reported cases of cholera in Sub-Saharan Africa and 
Latin America, with death rates of 3% and 1%, respectively. In 1994 WHO 
reported a decrease in the availability of clean water in several countries of 
Sub-Saharan Africa. Their estimates, based on the continuation of current 
trends, suggest that by the year 2025, the supply of renewable fresh water 
per person in the worst drought-affected countries of the continent will 
represent 15% of the 1955 values (WHO 1994). In many developing 
communities, water related infections caused by poor biological drinking 
water quality or lack of water supply are the most urgent public health 
issues. The water related infections are acute, tending to act quickly, 
causing illness and sometimes death. However, the chemical quality of 
water is also of growing concern. 

In the 1970s it was discovered that disinfection by chlorination of 
water containing humic substances generates chloroform and other 
trihalomethanes (THMs). THMs are known animal carcinogens (Clark 
1992; Glaze et al. 1993a; Moser 1992; Packham 1990; Stevens et al. 1989), 
raising concerns about chemical disinfection by-products and their 
toxicological effects on the population. 

Rachel Carson (1962) brought the issue of pesticide contamination of 
water and soil to the forefront. The growth of industry and the prevalence 
of agricultural pesticides and fertilizers s cause concern for the effect of 
these discharges on the chemical quality of water. An increase in 
motorized transportation leads to contaminated runoff and the potential for 
leakage of benzene, toluene and other aromatic hydrocarbons. These 
activities can have a severe impact on drinking water sources. The effect of 



chemical contaminants on public health is more often chronic, building 
over time and causing long term illness (Droste and McJunkin 1982). 

Standard water treatment techniques are very well defined in the 
United States and other developed countries. However, due to differences in 
economics and infrastructure, these treatments are not necessarily readily 
transferable from the developed to the developing world, including some 
lesser developed areas of developed nations. The operational and capital 
costs for this technology are often too expensive for developing 
communities. 

The development of community appropriate technology for treatment 
of drinking water is critical if universal access to a safe water supply is to 
be achieved. Utilization of available natural resources, where feasible, 
provides a greater opportunity for a sustainable drinking water supply. 
This requires innovative and creative technology. 

While no one technology can meet all of the needs of a community, 
solar photochemical oxidation holds promise as a viable alternative to 
standard, more expensive methods. The efficacy of the photocatalytic 
reaction has been demonstrated for biological contaminants (Block et al. 
1997; Ireland et al. 1993) and chemical contaminants (Blake 1994; Legrini 
et al. 1993). Therefore, it is reasonable to expect that the simultaneous 
destruction of both chemical and biological contaminants can be 
accomplished, although it has not been reported. While some 
investigations of simultaneous disinfection and detoxification with dye 
photosensitization have been undertaken (Acher 1984; Acher and 
Rosenthal 1977; Eisenberg et al. 1987a; Eisenberg et al. 1986), these 



processes have not been optimized, nor have they been compared directly 
with photocatalysis. The success of previous studies indicates that solar 
photochemical technology, when properly integrated with conventional 
treatment, has the potential to address the technical issues of water 
treatment facing a community. 

Use of solar photochemical technology for water treatment has the 
potential to provide a solution which is technically, economically and 
socially acceptable, manifested by the following potential benefits: 

• The use of the sun as a primary driver results in a renewable and 
essentially free source of energy for the reaction 

• Photochemical oxidation results in complete destruction of 
pollutants, which is preferable to dissipation, concentration or 
change of form 

• Since very small quantities of sensitizer or catalyst are required, 
and little if any external energy besides the sun, the technology 
has the potential for low capital and maintenance costs 

• The process is easily adaptable to a small scale, and therefore, 
suitable for rural and suburban communities 

Theory of Photochemical Water Treatment 

Photochemical water treatment is an oxidation process which 
involves the use of a chemical as a catalyst or sensitizer for indirect 
photolysis of a contaminant within the water. When exposed to light of the 
appropriate wavelength, which is governed by the photochemical used, the 
photosensitizer or photocatalyst generates a reactive species, an hydroxyl or 



peroxy radical, which subsequently reacts with the contaminant species 
(Ollis et al. 1989; Schiavello 1988; Teichner and Formenti 1985). This 
indirect process opens a much wider range of contaminants to destruction 
by photochemical means than would be available using only direct 
photolysis. The photochemical water treatment processes evaluated herein 
are photocatalysis, photosensitization and a combination of the two. The 
distinction between photocatalysis and photosensitization is based on the 
nature of the photochemical used. 
Photocatalysis 

Photocatalysis, or photocatalytic oxidation, for water treatment 
applications refers to a heterogeneous oxidation reaction involving solid 
semiconductor surfaces. The reaction occurs via the irradiation of a 
semiconductor catalyst, such as titanium dioxide (Ti0 2 ), zinc oxide (ZnO), 
or cadmium sulfide (CdS), with visible or ultraviolet (UV) light. The 
reaction is possible because of the structure of the semiconductor. The 
optical bandgap of a semiconductor is an area devoid of energy levels, 
between the highest occupied energy band, the valence band, and the lowest 
unoccupied energy band, the conduction band. When a semiconductor 
absorbs light with energy greater than the energy of the semiconductor's 
optical band gap, photoexcitation results (Bahnemann et al. 1991; Mills et 
al. 1993). For example, since Ti0 2 has an optical band gap energy of 3.2 eV, 
absorption occurs with light of wavelengths less than 388 nm, ultraviolet 
light, as indicated by equation 1-1 (Zhang et al. 1994b). 



x = ^ 



^(6.625xl(r 34 Js)(3.0xl0 10 cm /p 



3.2eV 



x| leV 5 I 

ll.6xl(T 19 J ' 



J 



The resulting excitation leads to the promotion of excess free 

electrons, e~, to the conduction band, leaving positive "holes," h + , in the 

valence band, referred to as electron/hole (e~/h + ) pairs. Equation 1-2 
describes this process (Carey and Oliver 1980; Oliver and Carey 1986). The 
electrons and holes are highly energetic and very mobile (Turchi et al. 
1989). 

Ti0 2 + hv =* h + + e~ ( 1-2 ) 

There are two paths that the e~/h + pairs can take. They can either 
recombine and deactivate, or migrate to the surface of the semiconductor 
and react with surface species as shown in equations 1-3 to 1-5. Figure 1-1 
is a graphical representation of this process for a single semiconductor 
particle. 

OH' + h + -> OH" ( 1-3 ) 

H 2 (ads) + h + -> OH" + H + ( 1-4 ) 

e~ + 2 -> HO; - ( 1-5 ) 

If reactions 1-3 to 1-5 take place, reactive species are formed, which 
in turn are able to oxidize organic contaminants in the water. The less 
recombination which takes place, the more efficient the semiconductor is 
as a photocatalyst. 






The peroxy radical, HO^, disproportionates further to form more 

hydroxyl radicals, OH', which combine with organic substrate to form 
oxidation products as shown in reaction 1-6 (Blake et al. 1991; Ireland et al. 
1993; Oliver and Carey 1986). If enough catalyst and light are present, a 



OH' + substrate — > oxidation products 



(1-6) 



pseudo chain reaction occurs resulting in complete mineralization of 
organics. It is thought that the process for the destruction of biological 
substrate is very similar, with the oxidation of proteins, lipids or nucleic 
acids resulting in inhibition of respiration or growth of the microorganism 
(von Sonntag 1987). 



hv > 



Reduction 



Electron Energy 




Adsorption 
of6 2 



Adsorption 



ofH 2 



Oxidation 



Figure 1-1. Graphical Representation of the Generation of e~/h + Pairs and 
Recombination by Photocatalytic Reaction on the Surface of a 
Semiconductor Particle; After Bahnemann et al. (1991) and 
Tseng and Huang (1990) 



8 

Photosensitization 

Sensitized photolysis, also referred to as photosensitization or 
photodynamic action, is another method of indirect photolysis very similar 
to photocatalytic oxidation. In photosensitization, energy is transferred 
from a photochemically excited molecule to an acceptor. The sensitizer (S), 
often a dye, absorbs light and is photochemically excited to a higher energy 
state. This process may offer an advantage over the photocatalytic process 
because the sensitizers can absorb light in the visible spectrum, allowing 
for use of a greater percentage of available sunlight. The reaction proceeds 
via the triplet excited state, owing to its longer lifetime relative to the singlet 
excited state (Foote 1968; Larson et al. 1989) as shown in equation 1-7. 

S + hv -» "S* (excited singlet) -» 3 S* (excited triplet) ( 1-7 ) 

The excited sensitizer (S*) then transfers some of its excess energy to 
an acceptor, forming a reactive, transient form of oxygen, singlet oxygen, 
l 2 (Larson and Weber 1994). Acceptors can be either organic material 
(OM) or dissolved inorganic species such as molecular oxygen, 2 . The 
intermediate reactive species produced from the reaction of the triplet 
sensitizer with organic material subsequently reacts with atmospheric 
oxygen under aerobic conditions (equation 1-8). 

3 S* + OM -> transient specia + 2 -> oxidation products + S ( 1-8 ) 

When the S* transfers its excess energy to molecular oxygen instead 
of OM, the oxygen molecule changes from its ground electronic state, the 
triplet state ( 3 Z g 2 ), to the excited singlet state, l 2 . The organic matter is 



then oxidized by the '0 2 to form oxidation products. Acher and Rosenthal 
(1977) described the mechanism by reactions 1-9 and 1-10: 

3 S* + :, X K 2 -^ S + '0 2 ( 1-9 ) 

'0 2 + OM -» oxidation products ( 1-10 ) 

When '0 2 combines with unsaturated organic compounds (UC), it 
yields free radicals which readily combine with nucleic acids, lipids and 
proteins for destruction of microorganisms as demonstrated by reactions 1- 
11 to 1-13 (Acher and Rosenthal 1977). 

'0 2 + UC -> ROOR -* RO* ( 1-11 ) 

RO'+RH^ROH + R* (1-12) 

R' # + 2 ->ROO\etc. (1-13) 

The wavelength of light absorption is specific for each sensitizer. 
Methylene blue and rose bengal are widely used dye sensitizers which 
absorb in the visible region at X. max 668 nm and X. max 549 nm, respectively 

(Acher and Juven 1977). 

Ideal sensitizers are defined as those compounds which exhibit the 
following criteria (Acher and Rosenthal 1977): 

• induce reactions with visible light, 

• are chemically stable during radiation or degrade to a sensitizing 
species, 

• are free of reactive functional groups, 



10 

• have good light absorption capacity, and 

• are soluble in water but easy to remove. 

Compounds which exhibit these qualities most efficiently are dyes, 
such as fluorescein and phenothiazine derivatives, flavins, certain 
porphyrins and polycyclic aromatic hydrocarbons (Foote 1968). For the 
purposes of water treatment, the latter two are too toxic; however, the 
others are acceptable. The sensitizers which have shown the most promise 
for both disinfection and detoxification, and which were evaluated for this 
research, are methylene blue and rose bengal. These dyes have been found 
to be relatively easily removed by precipitation with bentonite clay (Acher 
and Rosenthal 1977). 

The Solar Resource 

The sun can be modeled as a blackbody with a steady-state 
temperature of 5800K, radiating approximately 6.416 x 10 7 W/m 2 from its 
surface (Wieder 1992). The intensity of the sun's radiation on an object is 
inversely related to the square of its distance from the sun (Hsieh 1986). 
Since the distance of the earth from the sun varies throughout the year, the 
amount of sunlight reaching the atmosphere of the earth is not constant. 
However, a value termed the Solar constant, I sc , is the amount of solar 
radiation reaching a surface normal to the rays of sun outside the earth's 
atmosphere at a mean earth-sun distance of 1.5 x 10 11 m (Hsieh 1986). 
Based on measurements, the established value of the Solar constant is 1377 
W/m 2 (Randall and Bird 1989). Solar radiation reaching the atmosphere of 
the earth emits energies of wavelengths from gamma to radio, with most of 



11 

it concentrated in the visible region. The spectral distribution of the solar 
radiation outside the earth's atmosphere is given in Table 1-1. 



Table 1-1. Spectral Distribution of Solar Radiation 

Wavelength (jim) 
0.00- 0.395 (gamma to ultraviolet) 
0.40 - 0.70 (visible) 
0.71 - 2.00 (near infrared) 
2.00 - °° (infrared to radio) 
Source: Thekaekara ( 1976) 



■.-.-.-.-.-.-.-. -.-.-.-.-.-.-.-^.-.•.-.-.•.■.-.■.-.■.v 



■.■:•:■:■:■:•••:•:•:•:■:•:•••:•:•:•:•>: 



% of Total 
8.24 

38.15 

45.61 

6.51 

■:v->>xo:-:-:-:-:-v.:.:-:.:ox-:-:-:-:-:-:->x-:^^ 



The amount of solar radiation, also referred to as insolation, 
available at the earth's surface at a given time is dependent on the 
prevailing climatic conditions, the level of atmospheric pollution and the 
angle at which the sun strikes the surface (Hsieh 1986). Scattering and 
absorption of radiation, due to the presence of ozone, gas molecules, 
particulate matter and water vapor (including clouds), account for a 
significant reduction in the solar radiation incident on the earth's surface 
(Barry and Chorley 1992). The path length of the solar radiation in the 
atmosphere, which changes with the time of day and latitude, determines 
the amount of extinction of radiation by these parameters (Hsieh 1986). 
Approximately 4-6% of the solar radiation reaching the earth's surface is in 
the ultraviolet wavelength range (Goswami 1995). The remainder of 
incident radiation is in the visible and near infrared range. Using 
historical weather data the direct beam incident radiation for a given 
location in space and time can be calculated with reasonable accuracy 
(Randall and Bird 1989). 












12 

The photochemical oxidation process is governed by the absorption of 
light within the wavelength of effectiveness of the catalyst or sensitizer 
used. For the Ti0 2 photocatalytic process, the ultraviolet part of the 
spectrum, wavelengths below about 390 nm, is the most critical (Goswami 
1995). This process, therefore, is well suited for areas where cloudiness 
prevails, as the ultraviolet light is often present both as scattered and direct 
beam radiation. 

Photosensitization works with visible light, which is the greater part 
of direct beam incident radiation. The sensitizers evaluated in this work, 
methylene blue and rose bengal, are most effective in the blue (~ 670 nm) 
and red (~ 550 nm) ranges, respectively (Acher and Juven 1977). 

Research Objectives 

There exists a need for research, at all levels, tailored to address the 
needs of smaller, and possibly lesser developed, communities. The direct 
transfer of technology from one community to another is one of the 
solutions. However, it cannot serve as a replacement for the development of 
regional and community specific technology to solve regional and 
community specific problems. 

In order for this more localized technology development to occur, 
however, the information base must be expanded. One primary method for 
the appropriate expansion of the information base is the conduction of 
research which is more focused on the needs specific to these communities. 
The investigation of basic techniques, technologies and processes which 



13 

may differ from the mainstream is key to the provision of tools necessary for 
the advancement and development of all communities. 

The research reported herein is an effort to add some knowledge to 
that information base, and addresses two key areas of photochemical 
technology: 

• simultaneous treatment of chemical and microbiological 
pollutants, 

• comparative efficacies of photosensitization, photocatalysis and 
combined photosensitization and photocatalysis, 

While the research reported herein is not a solution to the problem of 
water supply, it is anticipated that the knowledge derived from this 
research could be applied to accept or reject one option, photochemical 
treatment, as a partial solution. In the process of creating a better reality, 
the best that one can wish for is options and the information to adequately 
evaluate those options. 















CHAPTER 2 
REVIEW OF SOLAR BASED WATER TREATMENT 

The use of sunlight for water treatment is not a recent phenomenon. 
Documented evidence for solar distillation systems exists as far back as 
1551 when Arab alchemists used glass vessels and concave mirrors to 
distill water (Malik et al. 1982). However, technologies for solar based water 
treatment have changed dramatically in recent years. The development of 
photochemical technologies have significantly expanded the application 
potential for solar based water treatment processes. What follows is an 
exploration of the various methods of water treatment which use solar 
energy as the primary driver, and a review of the current state of related 
research. 

Solar based water treatment processes can be roughly categorized as 
either physical or chemical. Physical processes are those processes which 
use the sun as a source of heat energy. Distillation and heat pasteurization 
fall into the physical process category. The chemical processes are those 
which involve a chemical reaction either directly or indirectly induced by 
light. These photolytic processes include ultraviolet disinfection and a 
number of photochemical processes. 



14 



15 
Physical Processes 

Distillation Processes 

The most studied solar based water treatment process is desalination 
by distillation. Solar distillation involves the use of sunlight to evaporate 
saline or brackish water for the purpose of collecting the desalinated 
condensate. Two approaches have been taken in the development of solar 
distillation units. The first, and more conventional, involves the direct 
absorption of solar energy by saline water, called passive solar distillation. 
The second, active solar distillation, is similar to a standard chemical 
distillation process using sunlight as the heat energy source for indirect 
heating of the water. In this type of unit, evaporation is in a centralized 
facility (Malik et al. 1982; Rajvanshi 1979). 
Passive distillation 

Passive solar distillation is easily understood when compared to the 
natural process of the hydrologic cycle. In the hydrologic cycle, the sun 
provides energy which warms the water of the oceans and other large 
water bodies, causing evaporation. Convective wind energy transports this 
vapor into the atmosphere where it condenses and produces precipitation. 
The precipitation either directly, as rain, or indirectly, as melted snow, 
recharges fresh water sources: lakes, rivers, streams, underground 
springs and groundwater aquifers. 

The solar distillation process is a simulation of this process in 
manufactured facilities. The sun warms the collected body of saline or 
brackish water and causes evaporation. The water vapor is carried by 



16 

convective winds, induced by the appropriate construction, and, upon 
cooling, the vapor condenses as pure distilled water. 

The conventional design for passive distillation systems is the basin- 
type solar still (Figure 2-1). The bottom surface of the basin is black to 
enhance the absorption of radiation by the saline or brackish water, 
supplied either continuously or batchwise (Malik et al. 1982; Rajvanshi 
1979). The basin is covered with a transparent, air tight cover which slopes 
downward to facilitate transport of the condensate as a thin film into a 
collection trough (Malik et al. 1982; Rajvanshi 1979). Solar radiation 
penetrates the cover, generally glass or plastic, and is absorbed by the 
water, warming it to induce evaporation. The temperature differential 
between the cover, which does not absorb much radiation, and the water 
surface leads to air convection currents which move the water vapor to the 
underside of the cover. The cool temperatures of the basin cover, relative to 
the water temperature, cause condensation, and the water forms a thin 
film which is collected via troughs. Basin stills can be either shallow or 
deep, depending upon the design and operational requirements. Shallow 
basins stills have water depths ranging from 1.25 cm (0.5 in) to 5 cm ( 2 in) 
and deep basin still water depths range anywhere from over 5 cm (2 in) up 
to 91 cm (3 ft) (Rajvanshi 1979). 

The first modern commercial solar still was installed in 1872 in the 
northern part of Chile, designed by Swedish engineer Carlos Wilson. The 
glass covered basin type solar still was 4700 m 2 and operated for many years 
treating feedwater with a salinity of 140,000 ppm (Howe and Tliemat 1977; 
Malik et al. 1982). Work conducted at the University of California's 



17 

Engineering Field Station in Richmond, California, concentrated on 
reducing capital costs and improving efficiency of the basin still by 
changing the geometric configuration. Designs tested included a circular 
still, several trough type stills with rounded or v-shape bottoms and 
stairstepped stills. The general conclusion of this work was that the basin 
type solar stills were not economically competitive in any of the tested 
configurations (Howe and Tliemat 1977). 



Solar 
Radiation 



Glass Cover 



Collection 
Troug 




Saline Water In 



Basin Water 




Condensate 

Film 



convective 
Winds 



Distillate 
Out 



Blackened Basin Bottom 



Brine Out 



Figure 2-1. Conventional Passive Solar Basin Still; After Malik et al. 1982 

and Rajvanshi (1979) 



At the University of Florida's Solar Energy and Energy Conversion 
Laboratory, Rajvanshi (1979) evaluated the efficacy of dyes as a means of 
increasing the efficiency of solar distillation. Using deep basin stills he 
added dye to saline water to increase radiation absorption and alter the heat 



18 

transfer rate. Three dyes, black napthylamine, red carmoisine, and a dark 
green mixture were used. The water treated with up to 500 ppm dye had an 
increased output of as much as 29% on clear days, however, no increase in 
output was observed with the dyes on completely cloudy days. Both the red 
and green dyes degraded when exposed to sunlight, however, the black dye, 
which also exhibited the largest increase in evaporation rate, did not visibly 
degrade with exposure to sunlight. 

Other research has focused on developing and improving the 
conventional basin type passive still. What emerged was the tilted tray solar 
still, wick solar stills, and double basin stills (Al-Karaghouli and Minasian 
1995; Higazy 1995; Howe and Tliemat 1977; Malik et al. 1982). 

The tilted tray solar still is a variation of the basin type solar still in 
which the basin is broken into a series of narrow strips arranged like steps. 
Each strip is on a different elevation, bringing the water surface much 
closer to the transparent cover, and increasing the operating efficiency. 
Generally these types of stills have very shallow basins. While the 
efficiency is increased, so is the capital cost, making this type of still 
infeasible for commercialization (Howe and Tliemat 1977). 

Wick still designs utilize an absorbent material (wicking), usually 
black to absorb radiation, as a facing on a glass covered inclined plane. 
Saline water is introduced along the upper edge of the inclined plane and 
trickles down saturating the wicking. The primary difficulty with this 
design is an inability to maintain a uniformly wet surface (Howe and 
Tliemat 1977). 


















19 

Double basin stills utilize the latent heat of the condensing water 
vapor, thereby increasing the daily yield over the conventional basin design. 
The double basin still has two transparent covers. The inner glass cover 
acts as a second, very shallow basin, with water running over it like a thin 
film from a pipe in the center. The heat from the water condensing on the 
underside of the lower basin cover is used to aid vaporization of the water 
on the topside, which then condenses on the upper cover. The distilled 
water is drained and collected from the underside of both transparent 
covers (Malik et al. 1982). 

During World War II Dr. Maria Telkes designed an inflated plastic 
still for use with the life rafts of the United States armed forces (Howe and 
Tliemat 1977). The design was similar to the basin still, however, it 
utilized a saturated sponge as the absorption media, and the entire 
assembly was designed to float on top of the water. Distillate was collected 
in a bottle at the bottom of the unit. These types of stills were referred to as 
floating sponge solar stills and reportedly over 200, 000 of them were 
produced during the war (Howe and Tliemat 1977). 

Higazy (1995) reported on the design and performance of a floating 
sponge solar still for desalination of sea water. The still design was based 
on the original design by Telkes. In Higazy's design water was pumped 
into the bottom of the still and constituted the bottom layer. Above that layer 
was a plastic sponge covered with a black cloth, which was where the 
radiation was absorbed and then transferred by conduction to the sea water. 
He examined two still designs, a single sloped cover which used mirrors to 
increase the radiation absorption area and double sloped cover, evaluating 



20 

the parameters of insolation intensity, temperature and the sponge 
properties (thickness and density). The primary improvement of this 
system over Telke's was that the use of plastic parts eliminated the problem 
of corrosion. 

Higazy's experiments were conducted using tap water and it was not 
indicated whether salts were added to simulate the saline environment 
produced by sea water, although the physical and behavioral properties 
were very similar. The design had no provisions for drainage of sea water 
or periodic removal of the salts from the still and or the sponge, and 
eventually problems might result from salt accumulation. 

Al-Karaghouli and Minasian (1995) developed a new type of passive 
solar still using a floating-wick and compared the still to conventional basin 
solar still and the tilted wick solar still. They also introduced azimuth and 
altitude tracking to increase the incident solar radiation on the still. The 
floating wick still was a conventional basin type solar still which contained 
a blackened jute wick floated on a polystyrene sheet. The unit floated no 
more than 0.5 cm above the still water level. The benefit of the floating wick 
still was due to the capillary action of the jute cloth, which was prepared in 
a corrugated shape to restrict salt accumulation to the upper parts. The 
stills used for comparison were made with the same materials and similar 
style to the floating wick for direct comparison. The floating wick solar still 
had a higher output than the other stills with which it was compared. 

The use of a corrugated shape solved the problem of scale formation 
and, due to the capillary action of jute cloth, the wick stayed uniformly 
wet. Consequently, in the summer months the floating wick still had a 



21 

higher output, versus comparable performance with the wick still during 
the cooler months. Tracking increased the output on all of the stills but was 
particularly impressive with the floating wick still, almost doubling the 
performance without tracking and having at least 30% higher output than 
the conventional basin still with tracking (Al-Karaghouli and Minasian 
1995). 

Solar distillation technology is fairly well established and has proven 
useful for small scale desalination of water. However, research has not 
advanced to the point where large scale processes are economically 
competitive with more conventional methods of distillation. 
Active distillation 

Active solar stills are those systems in which the sun's energy is 
captured external to the distillation system, either as thermal energy or 
photovoltaic electrical energy used to generate heat. In both cases the 
generated heat is then applied to the distillation unit. They can operate in 
conjunction with the conventional basin still, or they can be designed like a 
conventional flash distillation unit. Figure 2-2 shows a standard schematic 
for an active solar still which uses a solar collector and multistage flash 
distillation. 

Prasad and Tiwari (1996) conducted a thermal analysis of a 
concentrator-assisted solar distillation unit to optimize the inclination of 
the glass cover. They determined that the angle of inclination had an effect 
on the yield of this active solar distillation system, with an increase in yield 
which corresponded to an increase in the angle of inclination. For the 
climatic conditions studied (Delhi, India, latitude 28° N, longitude 77° E) an 



22 

angle of 75° was found to be optimal. The increased angle also led to a 
decrease in operating temperatures and evaporative heat losses. 

Solar Radiation 




^> 




Of 

u 

3 < 

* 5 

B 

m 




( s. 








r~^\ 




H 






\f p IV 




N/ 








CO 




T\ 


?apor T 

f N 




■ 










— i 


Heat 
Exchanseh 














fc 




r/ t^* 




V 


Brine FlashChambers 


Feed 






Could o: 
oi>jE Unit 




Saline 




Water '■ 



Figure 2-2. Schematic of Flash Distillation Using Solar Collector; After 
Malik et al. (1982) 



Farwati (1997) conducted a comparison of a multi-stage flash 
distillation system using solar energy input with flat plate versus 
compound parabolic collector (CPC) systems. The conditions used for 
evaluation were monthly average climatic conditions for Benghazi, Libya. 
Both collectors had an aperture area of one square meter. The compound 
parabolic collector was able to achieve a higher water temperature for entry 
into the flash distillation system (122°C vs 80°C) and a larger monthly 
average daily output with maxima of 64.9 liters for the CPC and 43.7 liters 
for the flat plate collector system in the month of August. Both systems 
operated with auxiliary heaters. Using the solar collectors alone, the CPC 
had a maximum monthly average daily distillate output of around 40 liters 
and the flat plate collector one of about 25 liters. 

Kumar and Tiwari (1996) compared performance of flat plate 
collector solar distillation systems in several operating modes. They 









23 

examined the systems with and without flow over the glass cover, operating 
in active versus passive mode and in double effect passive mode (i.e. second 
glass cover with water flow over the cover closest to the basin). They found 
that water flow over the glass cover gave the highest yield, as this decreased 
the condensation surface temperature and utilized the latent heat of 
condensation providing additional distillation. The system was a single 
basin solar still made of fiber-reinforced plastic, coupled with a flat plate 
collector and was really a hybrid of the passive and active system. The 
double effect mode did not enhance performance because of the difficulty of 
maintaining low and uniform flow rates over the glass cover. Tests were 
run with 1 m 2 area of cover and collector. On average the active mode with 
water flow yielded 7.5 liters per day, the passive mode yielded 2.2 liters per 
day, and the active without water flow yielded 3.9 liters per day. 

Sing and Tiwari (1993) evaluated and compared the yields and 
thermal efficiencies of those types of solar stills recommended for rural or 
urban applications The types of stills evaluated were: 1) passive single 
basin, 2) passive double basin, 3) multiwick single basin, 4) multiwick 
double basin, 5) active single basin and 6) active double basin. As 
anticipated, the double basin stills outperformed the single basin 
counterparts in both daily yield and thermal efficiency. Of the systems 
studied, the active double basin had the highest yield while the multiwick 
double basin had the best thermal efficiency. However, the use of the double 
basin was not recommended with high salinity feedwater (> 20,000 ppm). 
The multiwick single basin was suggested for moderate salinity (<1500 



24 

ppm) and the double basin designs were only recommended if technical 
personnel were not readily available. 
Pasteurization Processes 

Pasteurization, or thermal disinfection, is the application of heat for 
a specified time in order to destroy harmful microorganisms (Parker 1984). 
The pasteurization process is best known for it's use in the food and 
beverage industry, particularly for the pasteurization of milk. Recently, 
this technology has been examined for it's use for drinking water. In order 
to sterilize water by pasteurization, the water must be heated to a 
temperature of 72°C (161°F) for a minimum of 15 seconds (Cheremisinoff et 
al. 1981). Pasteurization can be obtained at lower temperatures, as low as 
55 - 65°C (134 - 149°F); however, the required residence time increases 
significantly as the temperature is reduced (Ciochetti and Metcalf 1984; 
Joyce et al. 1996). The lower temperatures are attainable by solar heating. 
One primary benefit of thermal disinfection over the photooxidation process 
is that light penetration is not required, thereby making it effective in high 
turbidity water. 

Andreatta et al. (1994) reviewed the use of pasteurization devices in 
the developing world with reference to several different styles of systems. 
The solar box cooker, solar puddles and flow through systems similar to 
solar hot water heaters have all been used as pasteurizers. 

The solar box cooker used as a pasteurizer is the least expensive, but 
also the most unreliable. A method for ensuring that the appropriate 
temperature has been reached is required and sometimes difficult to verify. 



25 

Another drawback is that it is strictly a batch method, so the water is not 
available throughout the day (Andreatta et al. 1994). 

A flow through device can be manufactured using readily available 
materials such as an automobile radiator thermostat valve and black 
painted tubing. The design is a simple heat exchanger, and several design 
variations have been tested. Flat configurations have been demonstrated to 
be more effective than tubular varieties, although the tube exchanger may 
be simpler to construct. The temperature control is very important, and the 
design is critical in order to have the appropriate residence time. The 
primary benefits of the flow through pasteurizer are the availability of 
water throughout the day, easier control and ability to process larger 
quantities of water (Andreatta et al. 1994). 

The solar puddle is a low cost large area device. It resembles a solar 
basin still in that there is a trough and a cover of clear plastic, however, 
since the water is not saline, there is no need to separate the condensate 
from the water in the puddle. For the puddle, determining that the 
appropriate water temperature and residence time is reached is difficult 
(Andreatta et al. 1994). 

Ciochetti & Metcalf (1984) evaluated the use of a solar box cooker 
(SBC) for pasteurization of water. They found that temperatures for milk 
pasteurization (65°C) for several hours were sufficient to kill most 
waterborne pathogens including viruses. Vertical temperature 

differentials were found within containers, and the position of both the jug 
in the SBC and the SBC itself had a significant effect on temperature and 
consequently sterilization. Tests were conducted in northern California 



26 

and required temperatures for pasteurization were reached for 
approximately six months of the year, from mid-March through mid- 
September. 

Joyce etal. (1996) investigated the thermal contribution of sunlight to 
the inactivation of fecal coliforms with both onsite testing and laboratory 
simulations. Their research was focused on the use of pasteurization for 
household systems. Using transparent 2-liter plastic bottles, of the type 
used for carbonated beverages, the water was heated to a temperature of 
about 55 °C, the same temperature recorded for 2-liter bottles of water in full 
sunshine in Kenya (latitude, 1°29'S; longitude, 36°38'E). Complete 
disinfection was obtained after 7 hours at 55°C. 

Burch and Thomas (1997) evaluated the feasibility of solar 
pasteurization for water treatment in developing communities, comparing 
it with other technologies traditionally employed in that arena. They 
concluded that solar pasteurization, preceded by roughing filtration for 
high turbidity water, was not economically competitive when compared 
with slow sand filtration, chlorination, and UV disinfection. However, it 
was the most effective of the four for a broad spectrum of microbiological 
contaminants and had the lowest maintenance requirements. Flow 
through solar pasteurization was slightly less costly than existing batch 
processes, and the cost could be reduced more with the use of a thin-film 
polymer system currently under study (Burch and Thomas 1997). 

Solar pasteurization is not a feasible method for large water 
purification systems, however, it shows clear promise for small remote 
communities, household needs or emergency situations in areas with 



27 

several hours of sunshine throughout the day. Pasteurization has the 
benefit of providing disinfection regardless of the turbidity of the water. One 
major hurdle is the ineffectiveness on cloudy days, which may be 
circumvented by having storage available and purifying larger quantities of 
water on clear days for cloudy day use. 

Photo Processes 

Experiments on the effect of sunlight on microorganisms were 
conducted as early as the late 19th century. Downes and Blount (1877) 
observed the disappearance of turbidity, as an indication of the presence or 
absence of microorganisms, from acidic urine placed in sunlight for 
several hours. Since that time, much has been learned about the effect of 
light, specifically ultraviolet radiation, on the inactivation of 
microorganisms. 

In the early 1900s direct photolysis by ultraviolet (UV) radiation was 
used for disinfection of potable water (Wolfe 1990). While this method was 
abandoned in favor of chlorination, problems with chlorine disinfection by- 
products have encouraged researchers to take another look at UV. Recent 
studies on the use of UV for drinking water have proven more successful 
(Slade et al. 1986; Wolfe 1990). Direct photolysis, however, only affects those 
species which can directly absorb light, primarily microorganisms. 

Indirect photolysis, photosensitization or photocatalysis, provides 
another alternative. When exposed to light of the appropriate wavelength, 
the photosensitizer or photocatalyst generates a reactive species, such as a 
hydroxyl radical or peroxy radical, which subsequently reacts with the 



28 

contaminant species. This opens a much wider range of contaminants to 
destruction by photochemical means and creates the possibility of 
simultaneous destruction of microbiological and chemical contaminants. 
Solar Disinfection 

Solar disinfection is direct photolysis by radiation from the ultraviolet 
spectrum (wavelengths shorter than 390 nm) sometimes referred to as 
photodynamic inactivation. Acra et al. 1990 have used sunlight for small 
scale disinfection of drinking water by direct photolysis of microbiological 
contaminants. Acra et al. (1990) postulated that a minimum solar UV-A 
intensity of 17.8 W/m 2 was required for 99.9% inactivation of fecal coliform 
based on field testing of solar disinfection reactors. The residence time 
required to reach these levels of inactivation ranged from 90 minutes to 2.5 
hours depending on the microorganism (Acra et al. 1990). The data 
indicated that a longer residence time, achieved by recirculation, lower flow 
rates, or increased reactor volume, could also lead to inactivation (Acra et 
al. 1990). They found that bacterial destruction wsa exponential as a 
function of solar UV-A intensity and time. The major problem encountered 
was the growth of phytoplankton in the reactor (Acra et al. 1990). 

In studies for the inactivation of Escherichia coli in sunlight, Shah et 
al. (1996) found that the rate of inactivation was related to the initial colony 
density. At very high initial densities of E. coli, inactivation was not 
sufficient for provision of safe drinking water. 
SQDIS 

A hybrid technology which combined the benefits of UV disinfection 
and heat pasteurization was proposed by Sommer et al. (1997). With the 



29 

SODIS reactors water was heated to a temperature of 50°C and subjected to 
solar UV-A providing both thermal and UV disinfection. Complete 
inactivation of fecal coliform in 2.5 hours was reported, even on completely 
cloudy days. The hybrid technology was more effective on the partly cloudy 
to completely overcast days when compared to pasteurization alone at 70°C. 
Halosol 

The halosol process is a combination of the use of halogens and 
sunlight developed at the American University in Beirut, Lebanon in the 
late 1970s to early 1980s. The process involves treatment with large doses of 
sodium hypochlorite or iodine solutions followed by exposure to radiation. 
The intended benefit is disinfection of small volumes of heavily polluted 
water followed by the removal of excess halogens for taste and odor control 
(Acra et al. 1990). 
Photocatalysis 

The most commonly studied indirect photolysis reaction for water 
and wastewater treatment is photocatalysis using titanium dioxide, Ti0 2 , 
as a catalyst. Laboratory, pilot and field studies have demonstrated Ti0 2 
catalyzed photodegradation of a wide range of organic chemicals (Table 2-1) 
including alcohols, aldehydes, alkanes, alkenes, amines, aromatics, 
carboxylic acids, dioxins, dyes, fuel constituents, halogenated 
hydrocarbons, herbicides, ketones, mercaptans, pesticides, polychlorinated 
biphenyls, solvents, surfactants and thioethers (Aithal et al. 1993; Das et al. 
1994; Ellis 1991; Goswami and Jotshi 1992; Legrini et al. 1993; Mills et al. 
1993; Ollis 1986; Zhang et al. 1994b). Several researchers have 



30 

demonstrated the inactivation of microorganisms in water by Ti0 2 
photocatalysis (Table 2-2). 

Table 2-1. Examples of Photocatalytic Treatment of Water and Wastewater 



Investigator (s) 


iCONTAMINANT(S) 


Catalyst 


iLowetal. (1991) 


Amines 


Ti0 2 


Abdullah et al. (1990) 


Aniline 


Ti0 2 


iGoswami et al. (1993) and Oberg (1993) 


Benzene, Toluene, Ethylbenzene 
jXylene 


, Ti0 2 




Chlorinated Aromatics 




Matthews (1986) 


■Chlorinated Benzenes 


mo 2 


jAhmed and Ollis ( 1984), Hsiao et al. 
(1983), Matthews (1986), Nguyen and 
:011is (1984), Ollis (1985), Pruden and 
iOUis (1983a), and Pruden and Ollis 
( 1983b) 


jHalogenated Hydrocarbons, 
Solvents (THMs, TCE, etc.) 


Ti0 2 

: \ 


Haradaetal. (1990) 


iOrganophosphorous Insecticides 


TiO,/Pt 


iAl-Ekabi et al. (1989), Goswami et al. 
! 1992 and Li etal. (1992) 


phenols & Chlorophenols 


Ti0 2 


jPehzzettietal. (1988) 


iPolychlorinated Dioxins and 
iPolychlorinated Biphenyls 


Ti0 2 ZnO, CdS, 
TiO,/Pt&Fe 2 3 \ 


Maillard-Dupuy et al. (1994) 
Pehzzettietal. (1990) 


Pyridine 

iS Triazine Herbicides 


mo 2 

Tio: 


Pehzzetti etal. (1989) 


Surfactants 


TiO : , 



Photosensitization 



The body of literature on the use of photosensitization for water 
and/or wastewater is much less extensive than that for photocatalysis with 
Ti0 2 . Most of the work with regard to microorganisms has been done in the 

medical field (Tratnyek et al. 1994). However, some work on virus 
inactivation and wastewater treatment was conducted in the early 1970s 
(Gerba et al. 1977a; Gerba et al. 1977b; Hobbs et al. 1977; Sargent and 
Sanks 1976). Recently, researchers have investigated the use of 
immobilized sensitizers for coliform destruction (Savino and Angeli 1985). 



31 



Table 2-2. Examples of Photocatalytic Treatment of Water and Wastewater 



Special 



ilNVESTIGATOR(S) 
:Blocketal(1997) 



Contaminants ) 
"Escherichia coli, Serratia 
■marcescens, 
Escherichia coli 



Catalyst \ Conditions 
fTi0 8 " 



Ireland et al. (1993), Wei 
let al. ( 1994) and Zhang et 
!al. (1994a) 



iMatsunaga et al. (1988) 
;Matsunaga et al (1985) 



Escherichia coli 



!Ti0 2 



Escherichia coli, Lactobacillus jTib 2 /Pt 
acidophilus, Saccharomycces 



__;: > 

immobilized 
bnembrane 
!Pt Loaded 
jcatalyst 






cerevisiae 



!Patel(1993) 



iBacillus stearothermophilus 
^spores, Escherichia coli, 
Micrococcus luteus, 
iPseudomonas aeruginosa, 
Serratia marcescens, 
■Staphylococcus aureus 



;Ti0 2 



[S aitoetal. (1992) 
iSjogren and Sierka (1994) 



Streptococcus sobrinus 
bacteriophage MS2 



:TiO, -Addition of Iron 



The remainder of the work on wastewater treatment has been 
conducted by only a few researchers working in concert. Their 
investigations on the treatment of wastewater and sewage effluents using 
methylene blue and rose bengal have shown that the technology was viable 
in laboratory, pilot and field scale demonstrations (Acher 1984; Acher et al. 
1994; Acher et al. 1990; Acher and Juven 1977; Acher and Rosenthal 1977; 
Eisenberg et al. 1987a; Eisenberg et al. 1986; Eisenberg et al. 1988). In 
addition to the microbiological contaminants, this work addressed 
wastewater and the specific industrial contaminant bromacil, indicating 
some viability for simultaneous treatment. The use of flavins was 
demonstrated for the destruction of herbicides and other organics such as 
phenol and aniline (Larson et al. 1989; Larson et al. 1991; Schlauch 1987). 
A brief summary of work in this area is shown in Table 2-3. 



32 



Table 2-3. Summary of Photosensitized Treatment of Water and Wastewater 


jlNVESTIGATOR(S) 


iCONTAMINANTS 


SENSITIZER(S) 


Conditions 


iAcher and Juven 1977 


^Escherichia coli 


MB.RB 


^oxidation pond 


: : 






^sewage water 


lAcher et al. 1990 


ifecal coliform, 


MB 


pilot plant - sewage j 




:enterococci, coliforms, 




iefYluents 




ipolio viruses 






iGerba et al. (1977a) and 


icoliform & polio virus 


MB 


sensitized for 24 h 


IGerbaetal. (1977b) 








iHobbsetal. 1977 


•coliform & polio virus 


MB 


> :• 


iSavino and Angeli 1985 


\E. coli 


MB, RB, eosin 


^Immobilized dyes 1 


Burkhard and Guth (1976) 


iTriazine Herbicides 


Acetone 


1 


Crosby and Wong (1973) 


2,4,5-T 


Riboflavin & Acetone 


\ I 


iHadden et al. (1994), and 


ip-cresol, phenol 


MB, rhodamine 6G, 


high pH (9-10) 


iSargent and Sanks (1976) 




neutral red, RB 


I 1 






malachite green, 




: 


\ 


hematoporphyrin-D, 


\ I 






L-hydrochloride, 


;i > 


: 


: 
1 


acridine orange & 


i i 


[ 




others 


\ \ 


ILarson et al. 1989 


aniline & phenols 


Riboflavin (RF) 


\ l 




;Triazine Herbicides 




iAcher and Rosenthal 1977 


ifecal coliform, COD, 


MB, RB 


berated sewage 




MBAS 


MB & RB(Algae, 


leffluents 


iAcher 1984 


iOrganics, E. coli, 


wastewater 




^bacteriophages, polio 


bacteria & viruses) 




1 


ivirus & algae 




; 


jAcheretal. (1994) 


isecondary effluent 
coliform & bromacil i 


MB 


[wastewater 




secondary sewage 








bffluent 



Summary 



In terms of effectiveness, the photochemical processes are preferable 
for overall water treatment to both the physical processes and straight solar 
disinfection, with the exception of desalination, with which it is not 
comparable. These processes are effective on both microbiological 
contaminants as well as on a wide range of chemical contaminants. 
However, in order for these methods to be commercially viable on a large 
scale, additional research must be conducted. There are three primary 



33 

areas where efforts should be concentrated: separation of the 
photochemical from the water, including immobilization, elucidation of 
harmful intermediates in lieu of complete mineralization and development 
of cost efficient or optimal operating parameters. For disinfection the 
photochemical processes compare favorably to solar disinfection, 
pasteurization, SODIS and halosol. Any of these process can be viewed as 
appropriate, particularly for household or small community applications. 
In locations where sunshine is in large supply and technically trained 
personnel and fossil fuels are in shorter supply, the use of solar based 
processes for treatment of water may prove to be a satisfactory alternative. 












CHAPTER 3 
EXPERIMENTAL DESIGN AND METHODS 

Choice of Experimental Parameters 

The performance of a photochemical reactor system is affected by a 
myriad of variables, only a few of which can be controlled. While the choice 
of photoreactant and the availability of light of the appropriate wavelength 
range are the two most critical variables, there are other, more subtle 
changes in reaction conditions that enhance or degrade the reaction 
efficiency. Both the concentration and the physical form of the catalyst or 
sensitizer have a marked influence on the efficacy of a given reactor 
(Matthews 1991; Wyness et al. 1994). Beyond those factors already 
mentioned, pH, the presence or absence of dissolved oxygen, reactor 
design, and the nature of the contaminants exhibit the most significant 
effect on process reaction rates (Acher et al. 1994; Bedford et al. 1993; 
Hadden et al. 1994; Kawaguchi and Furuya 1990). 

Development of the experimental design was predicated on analysis 
of reported work and preliminary experiments in consideration of the 
aforementioned variables. The choices made for the research reported 
herein regarding each parameter were noted at the end of the applicable 
section. 



34 



35 

Contaminants 

Some unique problems identified with groundwater throughout the 
United States Virgin Islands (USVI) served as a basis for the selection of 
contaminants for this study. Used as source for drinking water, much of 
the USVI groundwater is chemically contaminated with light 
hydrocarbons from leaking fuel tanks. 1 In addition, due to leakage from 
underground sewerage, the microbiological contamination is rather 
extensive. 2 A 1986 study of USVI waters found microbiological 
contamination in the form of Streptococcus, Klebsiella, Acinetobacter spp., 
Enterobacter, Pseudomonas, Salmonella and Escherichia coli (Canoy and 
Knudsen 1986). 

To simulate contamination from leaking fuel tanks, benzene, toluene 
and xylene were used as chemical contaminants. E. coli, Serratia 
marcescens and Pseudomonas aeruginosa were used as microbiological 
contaminants, indicative of the contamination identified by Canoy and 
Knudsen (1986), and what might be present from leaking sewerage. 
Catalyst Choice 

A number of semiconducting materials have been tested for use as 
photocatalysts in water and wastewater treatment. In order for a material 
to be effective for solar photocatalytic water treatment, it must be 
photoactive, able to use visible and/or near UV light, biologically and 
chemically inert, stable under irradiation, inexpensive, and non-toxic to 
humans and aquatic organisms (Carey and Oliver 1980; Mills et al. 1993). 



1 From private conversation with Bruce Green of Carribean Infratech. 

2 Ibid. 



36 

Several researchers have tested semiconductors for photoactivity, 
including barium titanate, BaTiO,, cadmium sulfide, CdS, tungsten oxide, 
W0 3 , titanium dioxide, Ti0 2 , zinc oxide, ZnO, and zinc sulfide, ZnS (Blake 
1994). On the whole, Ti0 2 is more active than the others (Blake 1994). 
Barbeni et al. (1985) evaluated four other semiconductor oxides relative to 
Ti0 2 for the photocatalytic degradation of pentachlorophenol and found 
photocatalysis to be the most efficient. In studies of the destruction of 
dichlorobenzene using ZnO, W0 3 , platinized Ti0 2 and untreated Ti0 2 , the 
Ti0 2 photocatalyzed samples reacted faster (Pelizzetti et al. 1988). 

Carey and Oliver (1980) evaluated several semiconductor oxides for 
stability under irradiation in neutral aqueous solution (Table 3-1). Of the 
semiconductors tested, only those containing titanium were found to be 
photostable. With an optical band gap of 2.4 eV, CdS is highly photoactive 
and excited by visible light, appearing to be attractive as a photocatalyst. 
However, as is typical for semiconductors which absorb visible light, it is 
not photostable and tends toward photoanodic corrosion (Davis and Huang 
1991; Mills et al. 1993). In the case of cadmium sulfide this leads to the 
precipitation of undesirable and ultimately toxic compounds, as shown in 
equation 3-1. 

CdS + 2h + -> Cd 2+ + Si ( 3-1 ) 

Considering all of the evidence Ti0 2 seems to be the most desirable for 
photocatalytic processes to date. Ti0 2 in anatase form is the most 



37 

commonly used, due to its chemical stability, ready availability and 
photoactivity (Blake 1994; Zhang et al. 1994b). 



Table 3-1. Photostability of Semiconductor Oxides Tested by Carey and 
Oliver (1980) 



Semiconductor 

BaTiOs 

CaTi0 3 

MgTi0 3 

SrTi0 3 

Ti0 2 (anatase) 

Ti0 2 (rutile) 

V 2 5 

ZnO 

ZnTiO, 



Photostable 
yes 
yes 
yes 
yes 
yes 
yes 

no 

no 
yes 






•:o:-:->:-:-r-:->>>>>:-:->>-:-:->>>:-:-:-:-:-x->xoc->x-:-xo:v-:-:->:->>:->>>: 



-:-:-:-:-:-:-:-:-:-:-:-:-:-:-:-:-r-r-»>r:-:->:-»x-»x- 



There have been a number of efforts to increase the efficiency of Ti0 2 
by surface modification of the catalyst or substitution doping. Loading of 
the Ti0 2 surface with noble metals has been used to enhance electron 
transfer (production of hydroxyl radicals) and to prolong the life of the 
oxidation site at the exterior surface (Blake 1994; Zhang et al. 1994b). 
Silver-loading of anatase Ti0 2 increases the efficiency for the destruction of 
chloroform and urea by 10% and 67%, respectively (Kondo and Jardim 
1991). Other metals used for surface modification are Pt, Rh, Cu, Ni and 
Pd. While these metals have been shown to increase efficiency, the cost and 
complexity of the surface deposition process are prohibitive for use in most 
communities. Substitution doping of Ti0 2 presents the same difficulty. For 
these reasons anatase Ti0 2 , Degussa P25, was used for this research. 
Choice of Photosensitizer 

In addition to the chemical criteria outlined previously for 
photosensitizers, they must also be inexpensive and non-toxic. Methylene 



38 

blue is the photosensitizer commonly used in water treatment research. It 
is preferred because it is inexpensive, absorbs preferentially at 670 nm, a 
wavelength which easily penetrates wastewater effluent, and has a very 
low toxicity. Methylene blue is administered orally in humans for 
medicinal purposes (Gerba et al. 1977b; Hobbs et al. 1977). 

Martin and Perez-Cruet (1987) evaluated a number of dyes for 
suitability as sensitizers. Using sterile sea water with a salinity of 28 ppt, 
twelve dyes were studied for absorption tendency by clams (Mercenaria 
mercenaria) and photodynamic action against Escherichia coli. Of the 
dozen dyes tested, five were considered suitable for further testing by 
Martin and Perez-Cruet, and rose bengal showed the most promise. Table 
3-2 shows the order of effectiveness of selected dyes against E. coli as 
determined by Martin and Perez-Cruet (1987). 

Other researchers have found methylene blue to be the preferred dye 
sensitizer, although rose bengal seems to work almost as well under most 
circumstances (Acher and Rosenthal 1977; Gerba et al. 1977b; Sargent and 
Sanks 1976; Savino and Angeli 1985). Several researchers (Larson et al. 
1989; Mopper and Zika 1987; Schlauch 1987) have investigated the use of 
flavin sensitizers. Their research suggests that riboflavin and lumichrome 
are both good photosensitizers. 

Acetone is the one other photosensitizer which seems to have given 
good results for water treatment. In tests for the photodecomposition of the 
herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), both acetone and 
riboflavin showed promise (Crosby and Wong 1973). Burkhard and Guth 



39 

(1976) also found acetone effective for the photodegradation of triazine 
herbicides. However, acetone is known to cause systemic effects when 
ingested by humans (Sax and Lewis 1989). 

Based on this information it appears that the research of 
photosensitizers is less conclusive than that for photocatalysts, warranting 
further testing. Therefore, both methylene blue and rose bengal were 
selected for further evaluation. 
Reactor Desig n 

The overwhelming majority of the research on reactor design for 
photochemical water treatment has been conducted for semiconductor 
photocatalysis, primarily with Ti0 2 (Blake 1994). However, since the 
reactions follow similar mechanisms, the same principles should apply to 
both photocatalysis and photosensitization. 

The two major reactor options are reactors using catalyst suspended 
in slurry or those in which a fixed supported catalyst is employed (Blake 
1994). While the bulk of the research for water and wastewater treatment 
has been conducted using slurries of titanium dioxide, there has also been 
a great deal of research in the area of immobilizing the catalyst using a 
number of different media, with varying results (Blake 1994). Benefits for 
the use of supported catalyst are the elimination of the need for separation 
and recovery of the catalyst and a possible increase in the reaction rate 
(Zhang et al. 1994b). 

Researchers at the University of Florida tested both flat plate 
photoreactors (Wyness et al. 1994) and shallow pond reactors (Bedford et al. 



40 

1993) for the destruction of 4-chlorophenol (4-CP) using Ti0 2 adhered to 
fiberglass mesh. They found that the same reactor systems performed 
better with the slurry catalyst than with the fiberglass mesh. For the flat 
plate configuration, reaction rates were two to five times faster (Wyness et 
al. 1994). 



Table 3-2. Order of Effectiveness of Dyes at 10" 4 M Concentration onE. Coli 
After 24 Hours Exposure to Light at Room Temperature 





Light Intensity 

i7 -2 -1 
utm sec 


E. coli colony coverage in quadrant areas 3 , mean ± SD 


Dye 


1 


2 


3 


4 


Control 


75 b 


8.7±0.5 


8.011.1 


4.512.0 


0.8 1 0.4 


Control 


300 c 


9.010.5 


9.010.5 


6.6 1 0.9 


1.210.4 


Rose Bengal 


75 
















300 














Erythrosine 


75 


7.011.4 













300 














Eosin Yellowish 


75 


6.012.8 


0.510.7 










300 


1.010.5 











Zinc Phthalocyanine- 


75 


7.011.4 


4.014.2 








tetrasulfonate 


300 










Acridine Orange 


75 


8.0 1 0.5 


1.510.7 


0.510.7 







300 


5.513.5 


0.5 1 0.7 








Methylene Blue 


75 


9.010.5 


4.510.7 


1.010.5 







300 










Fluorescein Sodium 


75 


9.010.5 


7.510.7 


3.510.7 


0.310.1 


Salt 


300 


8.510.7 


2.012.8 








Alphazurine A 


75 


9.010.5 


7.512.1 


1.510.7 







300 


9.010.5 


8.510.7 


4.512.1 


0.510.7 


Rosolic Acid 


75 


9.010.5 


6.012.8 


2.011.4 







300 










Alcian Blue 


75 


9.010.5 


7.510.7 


2.011.4 


0.510.7 




300 










Hematoporphyrin 


75 


9.010.5 


8.510.7 


4.513.5 


1.612.1 




300 


9.010.5 


8.510.7 


4.510.7 


0.810.4 


Alizarine S 


75 


9.010.5 


9.010.5 


4.512.1 


0.8 1 0.4 


Monohydrate 


300 


9.0 + 0.5 


9.010.5 


5.011.4 


1.010.5 



Streaked areas: 1, first streak; 2, streaks from first 

streak; 4, streaks from third streaks. Temperature, 
Martin and Perez-Cruet (1987). 



streaks; 3, streaks from second 
25°C. c Temperature, 28°C. Source: 



41 



Zhang et al. (1994) compared the performance of a number of 
different optimized catalyst support options with Ti0 2 slurry using a flat 
plate reactor configuration. Of those supports tested, all except glass beads 
performed as well as, or slightly better than, the slurry, with silica gel 
performing best. 

Hofstadler (1994) evaluated titanium dioxide-coated fused-silica glass 
fibers for the degradation of 4-CP and reported degradation rates 1.6 times 
higher than with Ti0 2 slurry. Some other silica based supports which have 
been evaluated were coated sand (Matthews 1991) and glass (Lu et al. 1993). 
Matthews found that suspensions of Ti0 2 coated sands were much easier to 
deal with in terms of separation, but were mass transfer limited. The 
work by Lu et al., using Ti0 2 supported on the inner surface of a glass tube 
reactor, indicated the possibility of catalyst reuse. 

Fox et al. (1994) examined the effect of zeolite supported Ti0 2 and 
Ti0 2 pillared clays on the degradation of alcohols and found a slight 
decrease in photoactivity relative to Ti0 2 slurry. Matsunaga et al. (1988) 
found Ti0 2 supported on an acetylcellulose membrane to be effective for the 
destruction of Escherichia coli. Other supports tested for Ti0 2 were 
activated carbon (Uchida et al. 1993), ceramic membranes (Aguado et al. 
1994), wood chips (Berry and Mueller 1994), metal, polymer, and thin films 
(Blake 1994). 

Some research has also been conducted on the immobilization of 
photosensitizers. Savino and Angeli (1985) examined the effectiveness of 
methylene blue, rose bengal, and eosin on polystyrene beads, and 



42 

methylene blue on granular activated carbon, silica gel, and XAD-2 
(polystyrene resin). They found that all of the immobilized dyes were 
effective for the destruction of Escherichia coli, but methylene blue on 
activated carbon was the most effective. 

Keeping the initial criteria in mind, ease of use and low operational 
and capital cost, a number of reactor designs were quickly ruled out. The 
methods for immobilizing catalyst all require fairly extensive preparation, 
including precipitation and calcination, in almost all cases. Therefore, the 
current research was conducted using suspended Ti0 2 and dissolved 
sensitizers. The question of the feasibility of immobilized catalyst and/or 
sensitizer was left for another study. 

There are a number of options available for the specific design of a 
reactor using slurry catalyst. In computer simulations of the destruction of 
TCE in batch flat plate and parabolic reactors, flat plate reactors yielded a 
larger treatment volume than did the concentrating and one-axis tracking 
parabolic reactors (Saltiel et al. 1992). Wyness et al. (1994) found that flat 
plate reactors were effective for chemical photodegradation with 
suspensions of titanium dioxide. Bedford et al. (1993) found that the 
shallow pond configuration was effective for the destruction of 4-CP. This 
minimalist configuration is attractive because of its potential for low capital 
and maintenance costs. 

For photosensitization the reactors have more closely resembled 
chemical reactors. Plug-flow reactors were successfully tested for the 
treatment of secondary effluent (Eisenberg et al. 1988), and continuous flow 
reactors showed promise in the sensitized photodegradation of 



43 

chlorophenols (Li et al. 1992). Acher et al. (1990; 1994) successfully used a 
series of tank reactors which were similar to the shallow pond 
configuration evaluated by Bedford et al. (1993). The laboratory reactors for 
this study were designed to mimic the shallow pond configuration. 
EH 

Ti0 2 is significantly affected by the pH of the aqueous solution in 
which it is suspended. Particle size and charge and the position of the 
valence and conduction bands are all a function of the pH of the solution 
(Mills et al. 1993). Block et al. (1997) found a neutral to acidic pH range best 
for the Ti0 2 photocatalyzed inactivation of bacteria. 

A number of researchers have investigated the effects of pH on the 
photocatalytic degradation rate of organics in aqueous suspensions 
(Bahnemann et al. 1991; Glaze et al. 1993b; Kawaguchi and Furuya 1990; 
Matthews 1986; Tseng and Huang 1990; Tseng and Huang 1991; Vidal et 
al. 1994). Kawaguchi and Furuya (1990) reported an increase in 
photocatalytic effect in acidic solution. The general consensus is that pH 
has little (no more than one order of magnitude) effect on the reaction rate, 
but that neutral pH provides the most efficient degradation. Other apparent 
pH effects are attributed to anionic effects from chemicals used for pH 
control. While pH was not a major factor in the photocatalytic reactions, it 
was necessary to seek an optimum pH for the simultaneous treatment of 
chemical and microbiological contaminants. In the research reported 
herein, photocatalytic experiments were conducted at neutral and acidic 
pH. 



44 



Photo sensitization is much more pH dependent. In studies of 
methylene blue photodisinfection processes, pH values ranging from 8.6 to 
10 were found to be optimum (Acher et al. 1994; Acher et al. 1990; Gerba et 
al. 1977b; Melnick et al. 1976). The same pH dependence was seen with 
methylene blue and rose bengal for the photodegradation of organic 
chemicals (Hadden et al. 1994; Li et al. 1992). In photosensitization of 
bromacil using methylene blue and rose bengal, reaction rates increased as 
pH values increased, with the highest rates at pH 9-10 (Eisenberg et al. 
1986; Eisenberg et al. 1988). Based on this information, the sensitizer 
experiments for this research were conducted in neutral and basic 
environments. 
Catalvst/Sensitizer Concentration 

The concentration of the photocatalyst and photosensitizer needed to 
be optimized in order to obtain meaningful comparison data. An optimum 
of 0.1% Ti0 2 concentration was found to be effective for BTEX by Goswami et 
al. (1993) and Oberg (1993). Patel (1993) and Block et al. (1997) found that 
0.01% Ti0 2 concentration worked best for the photocatalytic destruction of 
bacteria. Therefore a range of Ti0 2 concentrations, from 0.01% to 0.1% 
were tested in the laboratory in order to optimize the concentration for 
simultaneous photocatalysis. 

In pilot plant studies Eisenberg et al. (1988) found that concentration 
of methylene blue ranging from 1 to 10 mg/1 were sufficient for the 
photooxidation of bromacil. Acher and Juven (1977) conducted 
photosensitization experiments with sewage effluent and reported an 
increase in the destruction of coliforms with a corresponding increase in 



45 

methylene blue concentration, up to 5.0 mg/1. However, in pilot plant 
studies, smaller concentrations (less than 1.0 mg/1) were effective (Acher 
et al. 1994) and concentrations higher than 0.9 mg/1 methylene blue 
hindered light penetration (Acher and Rosenthal, 1977). The 
photosensitization screening experiments for this research were conducted 
at several levels of concentration, ranging from 0.01 mg/1 to 10 mg/1. 

Laboratory Experimental Desig n 

In this research full factorial designs were used for both the 
photocatalytic and photosensitization experiments. While the designs 
differed slightly the parameters tested were the same, catalyst/sensitizer 
concentration, pH, and light. A two dimensional control was imbedded in 
the experimental design by way of the dark experiments and the level with 
no photochemical. For the photocatalytic experiment four levels of catalyst 
concentration, two levels of pH, two levels of light, and redundant reactors 
were used, as shown in Table 3-3. For each of the two dye sensitizers tested, 
methylene blue and rose bengal, five levels of sensitizer concentration, two 
levels of pH, and two levels of light were used, as shown in Table 3-4. The 
photocatalytic experiments were repeated twice and the photosensitization 
experiments were repeated three times. 

In the combination experiments no pH adjustments were made. The 
experiments were conducted with 5 mg/L methylene blue and 0.01% Ti0 2 . 
Controls for this experiments were no photochemicals, Ti0 2 only and 
methylene blue only. The full design, repeated three times, is shown in 
Table 3-5. 



46 



Table 3-3. Design for Ti0 2 Photocatalytic Lab Experiments 



Contaminants 


Treatment One Treatment Two 
If EX and Bacteria If EX and Bacteria 


Light 


None 


None 


pH 


Neutral, 7 (±0.5) 


Acid, 4 (±0.5) 


Ti0 2 Concentration 


None 0.01% 0.05% : 0.10% 


None 0.01% 0.05% 0.10% 


Contaminants 


BTEX and Bacteria 


BTEX and Bacteria 


Light 


UV Lamps @ 29 W/m 2 


UV Lamps @ 29 W/m 2 


pH 

Ti6 2 Concentration 


Neutral, 7 (±0.5) 
None 0.01% 0.05% 0.10% 


Acid, 4 (±0.5) 
None 0.01% I 0.05% 0.10% 



Table 3-4. Design for Photosensitization Lab Experiments 



Treatment One 

If EX and Bacteria 

None 



Treatment Two 

If EX and Bacteria 

None 



Contaminants 
Light 



•; - 



pH 

Dye Cone, mg/L 
Contaminants 



>:•"-'•■-•-*-:-:•:---:-:->:-----:----•:-:-'-:-:--::-•-:-:•:-!-*-:•--------:-:.:.:-:■:-:>-:.:-:.:.; 



Basic, 10 (±0.5) Basic, 10 (±0.5) 

None [ 0.10 15 10 None 0.10 1 5 

M'X*x-:-:-x-:-:-:-:-:-:-:-:-:-x-x-:-:*:-:->^ 

BTEX and Bacteria BTEX and Bacteria 



! 10 



.:.x-x-x-x-x-x-x-x-:..xx-x<-"-x:-v-x-x-x*x-x-x> 



Light Sunlight 

pH Basic, 10 (±0.5) 



Sunlight 
Baric, 10 (±0.5) 



Dye Cone, mg/L 



:w:-:-:-:-:-:-:->:-;-;-;-;-:-:-x-:-:-:-:-:-:-:-: 



1 None \ 0.10 j 1 | 5 j 10 j None j 0.10 | 1 



:«»»»>>™ww:v:v:w:'^^^^^^^ 



10 



Table 3-5. Design for Combination Lab Experiments 



Contaminants 



Treatment One 
Iflx and Bacteria 



>:-:-X-X-:o:-:-:-v.:-:-:-:-y.:.:.;.v.:.: 



Treatment Two 
BTEX and Bacteria 



:•:•:■:■:■:■>:•:-:-: -»:-:-:-:-:-:-x-x-x-»:-:-: 



nmi Li gh t None None 

Photochemical j _Nope J0.O1% f iO^ 5 mg/L ."MB""" Both None:0j01%f iCv5 mg/L MBJIoSi 






Materials and Methods 



Reaction Vessels 

The photocatalysis reaction vessels were covered Pyrex dishes 
(Figure 3-1), which allowed light transmission above wavelengths of X > 300 



47 

nm, the shortest wavelength that reaches the earth's surface from the sun 
(Hsieh 1986). This filtered out the germicidal effects of the ultraviolet light 
which would not be present in naturally occurring sunlight. 



Water line 



60 



in in 




Lid removed to take 
samples 



100 mm 



Figure 3-1. Ti0 2 Reaction Vessel 



In order to eliminate problems of air stripping and ensure that the 
reactor was airtight, a slightly modified version of the photocatalytic 
reaction vessel was used for both photosensitization and the combination 
experiments. The reactor was equipped with a glass blown sampling port 
plugged with a butyl rubber septum and sealed with parafilm (Figure 3-2). 
The reactors were filled to the rim of the vessel in order to minimize head 
space. 



Bacterial Inoculation 

Cultures were prepared using trypticase soy broth nutrient, and 
incubated for 24 hours at 35°C. Three serial dilutions of 1:100 were 



48 

prepared using distilled deionized water. Photocatalytic reactors were 
inoculated with 400 \il ofE. coli, 400 \i\ of Serratia marcescens and 200 ul of 
Pseudomonas aeruginosa, using the 2nd dilution of each culture. 

Water line 



Parafilm to 
seal 



60 



£ 



mm 




Sample port 
with septum 



100 mm 



Figure 3-2. Photosensitization Reaction Vessel 



Only E. coli was used for photosensitization experiments, and the 
reactors were inoculated with 45 [i\ of the first dilution of the culture. In all 
cases the third dilution was used to confirm that the cultures were viable. 
This procedure is shown graphically in Figure 3-3. 



E.coli 
Slant 



£. coli culture 

in Trypticasc 

Soy Brot h 




Initial Count 
Agar Plate 
(Incu bated) 




photosensitization \ 



phoUKatalysis 



Experimental 
Glass Reactor 



Figure 3-3. Graphical Representation of Bacterial Inoculation 



49 

Initial bacterial densities in the reactors ranged from 10 3 to 10 4 

colonies per ml, with most values falling around 3.5 x 10 3 colonies per ml. 
Bacteria were obtained from American Type Culture Collection (ATCC). 
Reactor Chamber 

The reactor chamber was used for all of the photocatalytic 
experiments and the dark experiments for photosensitization. The 
chamber was a metal box equipped with 32 ultraviolet low-pressure 
mercury lamps and painted in flat black (Figure 3-4). The lamps were 
purchased from Southern New England Ultraviolet, model RPR-3500. The 
design output of the lamps was 3500A. Reactors were placed approximately 
35 cm from the light source, at which point the ultraviolet irradiation 
measured was 29 W/m 2 . External light was blocked via a hinged metal 
door which fit snugly over the chamber. The lamps were turned off for the 
dark experiments. 
Photocatalvsis Reactor Setup 

The reactors were loaded with deionized distilled and pH adjusted 
water and a combination of bacteriological and volatile organic chemical 
(VOC) contaminants, for a total volume of 100 ml. The chemical 
contaminants were approximately 1 ppm each of benzene, toluene and 
mixed xylenes, referred to as BTEX, and the bacterial species were 
Escherichia coli, Pseudomonas aeruginosa and Serratia marcescens. 
Redundant reactors were placed for two to four hours in a reactor chamber 
either with or without light. 



50 




Figure 3-4. Ultraviolet Light and Dark Reactor Chamber 



As shown in Table 3-3, four Ti0 2 concentrations were used for the 
experiments: 0.1%, 0.05%, 0.01% and none. The catalyst used was Degussa 
P-25. The water was adjusted to an acid pH (4.0 ± 0.5) and a neutral pH (7.0 
± 0.5) with hydrochloric acid and sodium hydroxide. After pH adjustment 
the water was autoclaved to remove any microbiological contamination. 
The 100 ml reactors were illuminated for 2 to 4 hours in the reactor 
chamber. 
Photocatalvsis Sampling and Analysis 

Samples for chemical analysis were taken prior to irradiation, after 5 
minutes, 15 minutes, 30 minutes and one hour of irradiation and at the 
same time intervals in the dark chamber. Samples were taken with a 
sterile syringe and placed directly into amber borosilicate screw cap vials 
with Teflon™ septa, and refrigerated until analysis. The samples were 
analyzed by a modification of the EPA purge and trap method using an SR 



51 

8610 gas chromatograph with PID detector (Abeel et al. 1994; Bellar and 
Lichtenber 1974; Oberg 1993). The method used was sensitive to a low 
concentration of about 1 ppb for the components in question. 

For evaluation of disinfection efficacy, duplicate petri dishes 
containing plate count agar nutrient were inoculated with 100 fil from each 
reactor. Two replicates were taken at 0, 30, 60, 120 and 240 minutes, 
yielding four counts for each set of conditions per experiment. The 
inoculated plates were spread and incubated for 24 hours at 35°C. After 24 
hours the number of bacterial colonies on each plate were counted. 
Photosensitization Reactor Setup 

The reactors were loaded with deionized, distilled, pH adjusted water 
and a combination of bacteriological and volatile organic chemical (VOC) 
contaminants to the top of the container, a total volume of approximately 
450 ml. The chemical contaminants were approximately 1 ppm benzene 
and 1 ppm toluene, referred to as BTEX, and the bacterial species was 
Escherichia coli, as noted above. The reactors were placed either in 
sunlight or in a closed, dark reactor chamber (Figure 3-4) for four hours 
and constantly agitated with a magnetic stirrer. 

As outlined in Table 3-4, five sensitizer concentrations of either 
methylene blue or rose bengal, were used for the experiments: 0.1 mg/1, 1.0 
mg/1, 5 mg/1, 10 mg/1 and none. Both the methylene blue and the rose 
bengal were purchased from Fisher Scientific. The water was adjusted to a 
neutral pH (7.0 ± 0.5) and a basic pH (10.0 ± 0.5) using sodium hydroxide. 
After pH adjustment the water was autoclaved to remove any 
microbiological contamination. 



52 

Photosensitization Sampling and Analysis 

A sterilized 10 ml syringe was used for taking samples via the 
sample port. Samples were taken at 0, 5, 15, 30, 60, 120 and 240 minutes by 
sterilized syringe and transferred into amber borosilicate screw cap vials 
with Teflon™ septa, and refrigerated in a standard commercial 
refrigeration unit until they were analyzed. 

For evaluation of disinfection efficacy, petri dishes containing plate 
count agar nutrient were inoculated, in triplicate, with 100 |il from each 
sample. Three replicates were taken per sample. The inoculated plates 
were spread and incubated for 24 hours at 35°C. After 24 hours the number 
of bacterial colonies on each plate were counted. Chemical analysis was 
the same as that used for Ti0 2 photocatalysis. 
Combination Experimental Setup. Sampling and Analysis 

The setup, sampling, and analyses for the combination experiments 
were very similar to that of the photosensitization experiments. The 
reactors were loaded with deionized, distilled water and a combination of 
bacteriological and volatile organic chemical (VOC) contaminants to the top 
of the container, a total volume of approximately 450 ml. The chemical 
contaminants were approximately 1 ppm benzene and 1 ppm toluene, 
referred to as BTEX, and the bacterial species was Escherichia coli, as 
noted above. The reactors were placed either in sunlight or in a closed, 
dark reactor chamber (Figure 3-4) for one hour and constantly agitated with 
a magnetic stirrer. 

As outlined in Table 3-5, four photochemical concentrations of 
methylene blue and/or Ti0 2 were used for the experiments: no 



53 

photochemical, 0.01% Ti0 2 , 5 mg/1 methylene blue, and 0.01% Ti0 2 and 5 
mg/1 methylene blue. 

A sterilized 10 ml syringe was used for taking samples via the 
sample port. Samples were taken at 0, 5, 15, 30, 60, 120 into amber glass 
screw cap vials with Teflon™ septa. The samples were refrigerated in a 
standard commercial refrigeration unit until they were analyzed. 

For evaluation of disinfection efficacy, petri dishes containing plate 
count agar nutrient were inoculated with 100 ul from each sample. Three 
replicates were taken per sample. The inoculated plates were spread and 
incubated for 24 hours at 35°C. After 24 hours the number of bacterial 
colonies on each plate were counted. Chemical analysis was the same as 
that used for Ti0 2 photocatalysis. 
Experim ents for Confirmation of Previous Work with Bromacil 

One set of experiments was conducted to confirm the previous work 
with photosensitizers in which methylene blue was used for the destruction 
of bromacil in wastewater. Duplicate photosensitization reaction vessels 
(Figure 3-2) were loaded with approximately 1300 ppb bromacil, 5 mg/L 
methylene blue and deionized water. After irradiation in sunlight for four 
hours, the reactor contents were analyzed by GCMS. The bromacil used for 
the experiments was tech grade obtained from E. I. DuPont de Nemours 
and Company, Inc. 






CHAPTER 4 
RESULTS AND DISCUSSION 

The results of laboratory experiments are presented and discussed in 
this chapter. The results are divided by experiment type: dye 
photosensitization, Ti0 2 photocatalysis and combination experiments. A 
general discussion is presented at the end of the chapter. Raw data for all 
experiments are contained in Appendix A. 

Dye Photosensitization 

Laboratory experiments were conducted to determine the effects of 
dye concentration and pH on the destruction rate of Escherichia coli and 
aromatic hydrocarbons (benzene and toluene) in sunlight. As described in 
Chapter 3, the experiments were conducted with the following treatments : 

• methylene blue (MB) and rose bengal (RB), 

• sunlight and dark, 

• pH 10 and pH 7, 

• 0,0.1, 1,5 and 10 mg/L of dye. 

In order to ensure reproducibility of the results, each set of 
experiments was conducted three times. A complete set of experiments 
was represented by one reactor for each of the sets of conditions highlighted 
above, for a total of 40 reactors per set. Five reactors were run at a time, 
each reactor containing a different concentration of a single dye (either 
methylene blue or rose bengal) with all other parameters the same. 

54 



55 

Samples were taken from each reactor at 0, 5, 15, 30, 60, 120 and 240 
minutes and refrigerated immediately. Three replicates were plated from 
each sample for microbiological analysis. The remainder of the 0, 60 and 
240 minute samples was refrigerated and saved for chemical analysis. 

For the experiments conducted in sunlight, the light was measured 
and recorded over the duration of the experiment, and ranged from 542 
W/m 2 to 892 W/m 2 . The average total insolation (incident solar radi ation) 
measured in each experiment is given in Table 4-1 and graphs of the total 
insolation are shown in Appendix B. 

Table 4-1. Insolation Measurements from Dye Sensitization Experiments 






Set Conditions Insolation, W/m 2 

#1 ' Methylene Blue, pH 7 685 

Methylene Blue, pH 10 671 

Rose Bengal, pH 7 746 

Rose Bengal, pH 10 715 

#2 Methylene Blue, pH 7 665 

Methylene Blue, pH 10 542 

Rose Bengal, pH 7 856 

Rose Bengal, pH 10 775 

#3 Methylene Blue, pH 7 892 

Methylene Blue, pH 10 696 

Rose Bengal, pH 7 841 

Rose Bengal, pH 10 749 



Experimental sets were conducted on different days, and though 
efforts were made to minimize the differences between sets, both solar 
insolation and initial contaminant concentrations did vary from one set to 
another. The mean, standard deviation, and range of these parameters for 
all experiments are shown in Table 4-2. 



OD 










Table 4-2. Descriptive Statistics of Measured Data for all Experiments 


MB Parameter 


Mean 


StdDev 


Min 


Max 


Sunlight, W/m 2 


692 


112 


542 


891 


Sunlight, pH 7, W/m 2 


743 


129 


665 


891 


Sunlight, pH 10, W/m 2 


641 


50 


542 


696 


Initial Coliform Density, cfu/L x 10 3 


784 


365 


27 


1453 


Initial Benzene concentration, ppb 


676 


210 


377 


1218 


Initial Toluene concentration, ppb 


314 


139 


136 


770 


:*>:v:v:-:-:-:v:v:-:v-:-:-x-:-:-:-:->:-:-:-x^ 


WflWMCWffWWWflMflWMWWI 








RB Parameter 


Mean 


StdDev 


Min 


Max 


Sunlight, W/m 2 


781 


56 


715 


856 


Sunlight, pH 7, W/m 2 


815 


60 


746 


856 


Sunlight, pH 10, W/m 2 


746 


30 


715 


775 


Initial Coliform Density, cfu/L x 10 3 


816 


375 


187 


1680 


Initial Benzene concentration, ppb 


560 


262 


296 


1407 


Initial Toluene concentration, ppb 


426 


226 


155 


1026 



The data, as well as the impact of each of the measured and 
controlled parameters, are explored in more detail below, and results are 
compared with the work of Eisenberg et al. 1987b, Acher et al. (1994), and 
Acher et al. (1990), for the photosensitized disinfection and bromacil 
destruction in secondary treated wastewater effluent. 
General Comments About Experimental Data 

The average standard deviation of the disinfection data was 25% for 
methylene blue experiments and 13% for rose bengal experiments (Table 4- 
3). Plates on which the colonies were not individually identifiable and those 
with severe contamination were not counted, which resulted in the loss of 
approximately 20% of the 840 plates in a given experimental set. Due to 
contamination of the incubator, all 105 of the plates from the sunlight, pH 
10, methylene blue experiment in set number two had to be discarded. In a 
few instances the samples were dropped and broken before they could be 
plated. 



57 

The initial (t=0) disinfection samples for the dark, pH 10, rose bengal 
experiment in set number one were abnormally, though consistently, low. 
The low values were attributed to not allowing time for adequate mixing in 
the reactors prior to drawing the first sample. Since the values were 
consistent from one reactor to the next, the data could not be treated as 
outliers, but accommodations were required for accurate interpretation. 
For this set of data, the fractional survival values were calculated using the 
5 minute instead of the zero minute samples. 

The average standard deviations of the detoxification data were 10%, 
or less, of the average values as shown in Table 4-3. Sample loss for 
detoxification occurred when the sample was dropped and broken prior to 
analysis, which occurred twice in experimental set number three. The 
samples on either side of the dropped sample, 8^, were analyzed, and the 
sample value for the desired time was interpolated. When the dropped 
sample was an initial sample, 33 , the 5 minute sample was substituted. 
Chemical samples were generally analyzed within two weeks of the 
experiment. 



Table 4-3. Average Standard Deviations for all Dye Photosensitization 
Experiments 



•^^^^^^^^^^^.■^.■.■.■.■.■.■.■^.■.■.■.■.•.•.■.■.■.•.■.■.■.■.■^rr^^>^>>^^-^^. 



Benzene (ppb) Toluene (ppb) E.Coli 

StdDev "Avg SWDev Avg ' ~%rfUytal 

Methylene Blue 51 578 29 375 — 

Rose Bengal 46 487 36 363 13 



.-.■.■.■.-.-.•.-.•.-.•.•:•:•;-:-:■:-:•:-.-.-.-. 



^^^r^^rrrrrrrr^.^^^>^^^.^^^------^^^^^r^^^^^- 



58 

Statistical Treatment of the Data 

Microsoft Excel version 5.0 for the Macintosh was used for statistical 
analysis of the data. For the more common calculations, including least 
squares linear regression, the functions available in the software package 
were used. All other values were calculated using the equations as noted 
throughout this section. 

Since the sample sizes were generally small (less than 30), the entire 
populations were used to calculate standard deviation from Equation 4-1. 



.o.J "£-'HZ->) 



(4-1) 
n 



For disinfection data analysis, the fractional survival and percent 
destruction of colony forming units (cfu) were used for reporting and 
analyzing the data. The values used for disinfection data analysis were 
obtained by taking the average of the plates for each sample collected within 
an experimental set, calculating fractional survival (or % destruction) and 
averaging those values across experiments for use. The data, obtained in 
this way for methylene blue at 30 minutes, are shown in Table 4-4. 

In situations where calculations resulted in a negative percent 
destruction, the percent destruction was set to zero. In some instances the 
fractional survival exceeded 2.0, specifically, the data from the dark, pH 10, 
rose bengal experiment in set one. For that data set, the fractional survival 
was calculated relative to the 5 minute samples, i.e. fractional survival = 
N t /N 5 . 



59 



Table 4-4. Mean Fractional Survival (± 31%) of E. coli @ t= 30 minutes in 
MB Experiments 



: 


_t# 


Sunlight pH 10 Sunlight pH 7 


Dark pH 10 


DarkpHT] 


i Control 


1 


0.000 0.172 


1.113 


1.500 


; 


2 


0.534 


1.013 


0.169 




3 


0.084 0.082 


0.364 


0.503 | 


[Average 

;0.1 mg/L 


1 


0.042 0.262 
0.000 0.013 


0.830 
0.592 


0.724 

VA»AV.W.'.*MV.'JV.V.V.wX 

1.547 


: 


2 


0.155 


0.841 


0.088 \ 




3 


0.009 0.000 


0.583 


0.540 


: Average 
;1 mg/L 


1 


0.005 0.056 
0.000 0.007 


0.672 
0.494 


0.718 

"a779"1 




2 


0.013 


0.538 


0.101 




3 


0.000 0.000 


0.000 


0.502 | 


| Average 




0.000 0.007 


0.344 


0.461 | 


[ 5 mg/L 


1 


0.000 0.002 


0.030 


0.000 


; 


2 


0.016 


0.007 


0.000 




3 








[ Average 




0.000 0.006 


0.039 
0.011 


0.158 


1 10 mg/L 


1 


0.000 0.016 


0.034 j 




2 


0.000 


0.000 


0.018 


! Average 


3 


0.000 0.000 


0.004 0.195 
" 0.005*1 ololSB j 

v.-.-.-.%%-.-.-.\-.-.*.-.'.*.'.'.-.'.-.-.-.'.v.*. - .-.'>.v.-.\%\%v.%-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-; 



Detoxification data were treated in a similar manner. The 
concentration data, as parts per billion (ppb), for each experimental set 
were normalized to the initial concentration (C t /C ). The normalized values 
were averaged across experimental sets. Since only one data value existed 
per sample for each experimental set, standard deviations were calculated 
across sets only. Outliers were identified using the ASTM recommended 
criterion for single samples (ASTM 1988) which uses the following test: 



T n = |(x-x n )|/s (4-2) 

The critical value of T n is a function of the number of observations and is 
obtained from a table (ASTM 1988). Using this criterion, one value was 
found to be an outlier at a significance level of 10% (5% for toluene) and 



60 

subsequently discarded. The outlying sample, the 240 minute, 1 mg/L 
sample from RB, dark, pH 10 in experimental set number two, was thought 
to have been poorly capped, resulting in volatilization of the sample prior to 
analysis. 

The data were viewed in several ways. An initial observation was 
conducted for the detection of trends and to determine if the desired effect 
was achieved. These trends were displayed as a function of time for all of 
the average values as x-y scatter plots. If trends of the desired effect, 
destruction of contaminants with time, were detected, the data were 
analyzed further for the impact of specific parameters on the final results 
as described below. 

Analysis of Means (ANOM) was applied to obtain a statistical 
snapshot of the effect of specific parameters on the outcome. In this 
method, mean values and statistical deviations were used to clarify the 
significance of each parameter. The ANOM is a variation on a process 
control chart and allows for the exploratory analysis of several parameters 
simultaneously (Mason et al. 1989). A relatively conservative a-level of 0.05 

was chosen to minimize the probability of false alarms. A smaller a-level 

was not desirable as it might have resulted in missed signals and would be 
inappropriate for this type of exploratory analysis (Wheeler 1990). 

The Pooled Variance Estimator was used for determination of 
Estimated SD (X) as shown below. Decision limits for the ANOM charts 
were calculated using the following equations (Wheeler 1990): 



61 

Estimated SD (X) = V? ( 4-3 ) 



n? *• * j on / vw Estimated SD (X) , . . . 

(Estimated SD ( X )) = r ( 4-4 ) 



UDL X = X + H (Estimated SD ( X )) ( 4-5 ) 

LDL X = X - H (Estimated SD ( X )) ( 4-6 ) 

where: 

s = standard deviation of X, 

X = average of observations in a subgroup, 

sr = average variance of X, 

n = number of observations per subgroup, 

X = grand average of all observations, 

H = ANOM critical value at a selected a, from table (Wheeler 1990), 

UDL X = upper decision limit, and 

LDL X = lower decision limit. 
Averages which were outside of the decision limits were considered to be 
statistically significant, and those parameters were determined to be 
influential 

In some instances the data were graphically represented. For this 
analysis, data were simply categorized according to the parameters of 
interest, and standard deviation and mean values were calculated using 
the Microsoft Excel functions. These values were then charted, either as 
scatter plots or bar charts. Where appropriate, least squares linear 



62 

regression, also using Microsoft Excel, was performed to identify specific 
trends and relationships. 

Where clear destruction of contaminants was seen, kinetics were 
considered. Results were fitted to first order kinetic equations, and 
experimental reaction rate constants were obtained for comparison to 
published data. This information is presented in the section on kinetic 
considerations, which includes kinetic data for all relevant experimental 
sets. 
Presenta tion of Results and Identification of General Trends 

While disinfection in the presence of aromatic hydrocarbons was 
achieved with both rose bengal and methylene blue, simultaneous 
detoxification was not observed with either dye. Under the conditions 
tested, the presence of MB increased the disinfection rate of water 
contaminated with E. coli over sunlight alone. 

MB photosensitized disinfection at pH 10 (Figure 4-la) appears to be 
slightly more effective than MB photosensitized disinfection at pH 7. At pH 
10, all MB concentrations resulted in at least a 99.5% coliform reduction 
after thirty minutes of irradiation, compared to 96% reduction with 
sunlight alone. With 10 mg/L MB, complete coliform destruction was 
achieved after only five minutes of irradiation. No coliforms appeared in 
any of the samples taken after irradiation began. The intensity of sunlight 
in these experiments ranged from 542 to 696 W/m 2 . 

Destruction at pH 7 was not quite as dramatic (Figure 4- lb). The 
coliform reduction after 30 minutes ranged from 99.5% with 10 mg/L MB to 
96% with 0.1 mg/L MB. Comparatively, only a 74% reduction was attained 



with sunlight alone. The intensity of sunlight ranged from 665 W/m 2 to 
891 W/m 2 . Differences between pH 10 and pH 7 cannot be attributed to 
differences in light intensity since, as shown in Tables 4-1 and 4-2, the 
intensity was greater in the pH 7 experiments even though less reduction 
was achieved. The difference in values for control reactors would lead one 
to conclude that any pH effect was a function of the general disinfection 
mechanism rather than of the photosensitization process specifically. 



(a) 




Avg S.D. = 14.5% 



15 30 45 

Time (minutes) 



60 



-♦- Control 
-B-0.1 mg/L 
-A-1 mg/L 
-X- 5 mg/L 
-X-10 mg/L 



100% 



(b) 







15 30 45 

Time (minutes) 



60 



c 


Control 




0.1 mg/L 




1 mg/L 


-X-5 mg/L 


-x- 


10 mg/L 



Figure 4-1. MB Destruction of E. coli in Sunlight; (a) pH =10, 1 = 542-696 
W/m 2 (b) pH =7, 1 = 665-891 W/m 2 



avg 



avg 



64 

In the presence of at least 1 mg/L MB and sunlight (542 - 696 W/m 2 ), 
complete disinfection occurred within 5 to 30 minutes. However, in the 
absence of MB with the same intensity sunlight, complete disinfection 
required at least 60 minutes (Figure 4-2). Complete disinfection did not 
occur at all in the dark, although a 99% coliform reduction was observed 
with 10 mg/L MB in the dark. Mean fractional values for the methylene 
blue experiments are presented in Table 4-5. 



(a) 




15 30 

Time (minutes) 



-t— 
45 



60 



No MB, Sunlight 
-No MB, Dark 



1 mg/L MB, Sunlight 
1mg/L, MB Dark 



(b) 




Avg S.D. = 28% 



15 30 45 

Time (minutes) 



60 



to MB, Sunlight 
-O- No MB, Dark 



1 mg/L, Sunlight 
1 mg/L, Dark 



Figure 4-2. Destruction of E. coli in sunlight with 1 mg/L MB- (a) pH =10 
I avg = 542-696 W/m 2 and (b) pH 7, 1 = 665-891 W/m 2 



avg 



65 



Table 4-5. Mean Fractional Survival (±25%) of E. coli in MB Experiments 

Control Sunlight pH 10 Sunjfcfrt pHT~" Dark pH 10 Dark pH 7 

Ng/N 1133 0.811 0J54 0671 

N 15 /N 0.707 0.428 0.626 0.493 

N 30 /N 0.042 0.262 0.830 0.724 

N 60 /N 0.000 0.013 0.681 0.858 

N 120 /N 0.000 0.000 0.449 0.063 

Nag/No 0.000 0.000 0.365 0.008 

6.1 mg/L ^T^T"™" 

N 5 /N 6.030 6.651 6,867 6.609 

N 15 /N 0.002 0.234 0.766 0.613 

N 30 /N 0.005 0.056 0.672 0.718 

N 60 /N 0.000 0.016 0.600 0.363 

N 120 /N 0.000 0.005 0.299 0.141 

N?4 p /N p 0.000 0.000 0.285 0.077 

1 mg/L 

N5/N 0MXT~" 0JL94 -™-^ggp-~-» - ~~—^ 

N 15 /N 0.000 0.011 0.581 0.657 

N 30 /N 0.000 0.007 0.344 0.461 

N 60 /N 0.000 0.006 0.223 0.312 

N 120 /N 0.000 0.002 0.040 0.329 

n ^/Nq aooo 0.000 0.006 o.osi 

5 mg/L 

n 5 /No a666™ H£666 ""06® 6T29? 

N 15 /N 0.003 0.014 0.118 0.209 

N 30 /N 0.000 0.006 0.039 0.158 

N 60 /N 0.001 0.002 0.039 0.139 

N 120 /N 0.000 0.002 0.000 0.160 

N 2 4o/N 0.000 0.000 0.005 0.012 

10 mg/L "" 

n 5 /n oooo 6.666 aooo 6376 

N 15 /N 0.000 0.010 0.002 0.160 

N 30 /N 0.000 0.005 0.005 0.082 

N 60 /N 0.000 0.002 0.002 0.076 

N 120 /N 0.000 0.000 0.000 0.023 

N24 p /N 0.000 0.000 0.005 0.052 



Rose bengal was less effective for photochemical disinfection than 
was MB. The presence of RB had little, if any, positive effect on the 
disinfection rate over sunlight alone, although the experiments at pH 7 
appeared to exhibit some photochemical disinfection (Figure 4-3a). 

In the experiments conducted at pH 10 (Figure 4-3b), RB had no 
positive effect on disinfection over sunlight alone. Coliform reduction of 



greater than 99.9% was observed by 60 minutes in sunlight alone; however, 
in the presence of RB the same coliform reduction was not evident until the 
240 minute samples with 0.1 mg/L RB and the 120 minute samples for all 
other RB concentrations. Coliform reduction was about the same by 30 
minutes regardless of the RB concentration, with a low of 81% for 10 mg/L 
RB and a high of 90% with 1 mg/L RB. The control, sunlight alone, had a 
coliform reduction of 88%. The differences are not significant, as all values 
fall within the average standard deviation of 21%. The average intensity of 
sunlight in these experiments ranged from 715 to 775 W/m 2 . 

As was evidenced in the experiments with MB, disinfection appeared 
to be less effective at the neutral pH value of 7 (Figure 4-3a). The exception 
was with the higher concentrations of RB, 5 and 10 mg/L (Figure 4-4), 
where coliform reductions by 30 minutes were 96% and 97%, respectively. 
In comparison, coliform reduction in sunlight alone (746-856 W/m 2 ) by 30 
minutes was 77%, 78% with 0.1 mg/L RB and 89% with 1 mg/L RB. Mean 
values for the fractional survival of E. coli in the rose bengal experiments 
are shown in Table 4-6. 

While some reduction in both benzene and toluene concentration was 
observed with both dyes under every set of conditions, there was a 
substantial amount of contaminant (130 - 550 ppb) remaining in the water 
(Tables 4-7 and 4-8) after four hours. Initial concentrations ranged from 
139 - 1400 ppb as shown in Table 4-2. Figures 4-5 to 4-8 show the 
concentration of benzene and toluene as a function of time at various dye 
concentrations. 






67 















(a) 




15 30 45 

Time (minutes) 



60 



-6— Control 
-O-0.1 mg/L 
-A-1 mg/L 
-X-5 mg/L 
-X-10 mg/L 



(b) 



100% 
90% 




AVG S.D. = 16.1% 



H ( 

15 30 45 

Time (minutes) 



60 



— o- 


Control 


— H- 


0.1 mg/L 




1 mg/L 




5 mg/L 




10 mg/L 



Figure 4-3. RB Destruction of E. coli in Sunlight; (a) pH = 7, 1 = 746-856 
W/m 2 (b) pH = 10, L, = 715-775 W/m 2 



The experimental values for both benzene and toluene in MB showed 
fairly consistent reductions, with normalized concentrations ranging from 
0.59 to 0.87 after four hours. Both the greatest and smallest reductions 
corresponded to control reactors, sunlight at pH 10 and dark at pH 7, 
respectively. 



68 



(a) 



100% 

90% 



c 
o 

o 

a 




Time (minutes) 



No RB, Sunlight 
-No RB, Dark 



-X- 5 mg/L RB, Sunlight 
--•—5 mg/L , Dark 




15 30 45 

Time (minutes) 



60 



-♦-No RB, Sunlight 
O No RB, Dark 



-X-10 mg/L RB, Sunlight 
G- 10 mg/L RB, Dark 



(b) 

Figure 4-4. RB Destruction of E. coli at pH =7, I avg = 715-775 W/m 2 ; 
(a) 5 mg/L RB and (b) 10 mg/L RB 



Examination of the normalized data (Tables 4-9 and 4-10) did not yield 
a different conclusion. Neither chemical contaminant exhibited a 
substantial difference in behavior between control and non-control reactors 
in either MB or RB experiments, as seen from Figures 4-9 to 4-12. 

In RB experiments reductions ranging from 15% to 36% for benzene 
and 24% to 47% for toluene in sunlight were observed. One reactor, the 
dark control reactor at pH 10, exhibited no reduction at all. However, since 
the other controls, both in sunlight and in dark, had destruction rates 



69 

which were in the middle of the range for the non-control reactors, this 
cannot be considered an indication that photochemical action took place. 

Table 4-6. Mean Fractional Survival (±13%) of E. coli in RB Experiments 
Ccmtroi Sunlight pH 10 Sunlight pH 7 Dark pH 10 Dark pH 7 



N 5 /N 


0.668 


0.714 


0.961 


0.925 


N 15 /N 


0.315 


0.458 


1.074 


0.729 


N 30 /N 


0.122 


0.226 


0.952 


0.762 


N 60 /N 


0.000 


0.001 


0.795 


0.527 


N 120 /N 


0.000 


0.000 


0.660 


0.512 


N 240 /N 


0.000 


0.003 


0.381 


0.331 


0.1 mg/L 










N 5 /N 


0.541 


0.599 


0.846 


0.717 


N 15 /N 


0.381 


0.216 


1.058 


0.545 


N 30 /N 


0.131 


0.221 


0.930 


0.649 


N 60 /N 


0.002 


0.006 


0.797 


0.696 


N 120 /N 


0.005 


0.000 


0.617 


0.552 


N 240 /N 


0.000 


0.000 


0.269 


0.451 


1 mg/L 


N 5 /N 


0.498 


0.624 


1.028 


0.436 


N 15 /N 


0.241 


0.462 


1.007 


0.678 


N 30 /N 


0.102 


0.110 


1.033 


0.530 


N 60 /N 


0.009 


0.001 


1.107 


0.625 


N 12O /N 


0.000 


0.000 


0.838 


0.499 


N 240 /N 


0.000 


0.003 


0.461 


0.292 


5 mg/L 










N 5 /N 


0.707 


0.562 


0.966 


0.681 


N 15 /N 


0.447 


0.371 


1.006 


0.970 


N 30 /N 


0.150 


0.044 


1.015 


0.693 


N 60 /N 


0.006 


0.007 


0.920 


0.650 


N 120 /N 


0.000 


0.000 


0.597 


0.820 


N 240 /N 


0.000 


0.000 


0.334 


0.640 


10 mg/L 










N 5 /N 


0.555 


0.516 


0.989 


0.746 


N 15 /N 


0.451 


0.365 


0.884 


0.551 


N 30 /N 


0.188 


0.029 


0.918 


0.537 


N 60 /N 


0.002 


0.000 


0.888 


0.666 


N 120 /N 


0.000 


0.004 


0.659 


0.490 


N 240 /N 


0.000 


0.000 


0.388 


0.478 



70 



Table 4-7. Benzene (±51) and Toluene (±29) Concentrations (ppb) in MB 
Experiments 



BENZENE 


Time (min) 


Sunlight pH 10 


Sunlight pH 7 


Dark pH 10 


Dark pH 7 


Control 





953 


609 


632 


630 




60 


686 


593 


565 


643 




240 


522 


545 


476 


545 


0.1 mg/L 





767 


622 


597 


646 




60 


578 


533 


583 


533 




240 


513 


482 


399 


495 


1 mg/L 





733 


642 


729 


705 




60 


643 


555 


521 


554 




240 


544 


527 


419 


500 


5 mg/L 





707 


658 


604 


662 




60 


626 


502 


562 


597 




240 


564 


418 


385 


491 


10 mg/L 





762 


583 


596 


679 




60 


567 


535 


565 


548 




240 


478 


456 


431 


483 


TOLUENE 


Time (min) 


Sunlight pH 10 


Sunlight pH 7 


"DarrpWlF 


„_j^__ 


Control 





499 


278 


269 


310 




60 


298 


250 


224 


312 




240 


214 


221 


176 


234 


0.1 mg/L 





358 


282 


264 


324 




60 


248 


217 


245 


243 




240 


210 


158 


141 


211 


1 mg/L 





326 


297 


319 


357 




60 


275 


235 


207 


256 




240 


226 


208 


157 


209 


5 mg/L 





330 


300 


261 


327 




60 


261 


215 


248 


281 




240 


230 


160 


131 


203 


10 mg/L 





347 


266 


255 


331 




60 


233 


225 


227 


261 




240 


183 


171 


155 


211 



The greatest apparent reductions seemed to correspond to higher 
initial concentrations and exposure to sunlight. This type of behavior 
would be consistent with benzene and toluene being trapped in the vapor 
space above the water line. Although head space was kept to a minimum, 
as the samples were drawn from the reactor, head space increased. 
Though temperature was not a consistently measured parameter, an 
increase in temperature was observed, probably due to sunlight and friction 



71 

from the magnetic stirrers. The combination of temperature and head 
space increase would necessarily lead to volatilization of the chemical 
contaminants in the vapor space. Spot temperature checks with 
temperature strips on the outside reactor glass yielded values in excess of 
96°F in sunlight. 



Table 4-8. Benzene (± 46) and Toluene (± 36) Concentrations (ppb) in RB 
Experiments 



BENZENE 


Time (min) 


Sunlight pH 10 


Sunlight pH 7 


Dark pH 10 


DarkpH7 


Control 





716 


746 


432 


497 




eo 


692 


557 


446 


466 




240 


499 


539 


447 


425 


0.1 mg/L 





542 


657 


478 


504 




60 


508 


541 


474 


440 




240 


463 


508 


371 


417 


1 mg/L 





593 


618 


463 


516 




eo 


533 


513 


399 


438 




240 


389 


504 


332 


379 


5 mg/L 





611 


646 


437 


515 




60 


516 


524 


434 


413 




240 


386 


476 


350 


365 


10 mg/L 





583 


635 


483 


461 




60 


420 


513 


438 


419 




240 


375 


483 


371 


341 


TOLUENE 


Time (min) 


Sunlight pH 10 


Sunlight pH 7 


Dark pH 10 


Dark pH 7 


Control 





543 


541 


279 


421 




60 


486 


415 


283 


385 




240 


338 


370 


289 


349 


0.1 mg/L 





401 


493 


318 


442 




60 


367 


394 


311 


387 




240 


310 


367 


250 


346 


1 mg/L 





427 


481 


307 


464 




60 


367 


374 


246 


368 




240 


259 


355 


195 


303 


5 mg/L 





458 


491 


294 


443 




60 


364 


373 


282 


338 




240 


246 


317 


206 


284 


10 mg/L 





416 


483 


323 


410 




60 


298 


375 


281 


349 



■:-:-:•:•:•:-:•:•:•:-: .> v.v.»:.» x-:-:-:-:-:-:-----:-:-:-:-:-:-:-:-: 



240 



255 



329 






223 



275 









72 



1000 






Control 




0.1 mg/L 


-x- 


1 mg/L 




5 mg/L 


— A- 


10 mg/L 



(a) 



60 120 180 

Time (minutes) 



240 



•Referenced to internal 
standard, chlorobenzene 



(b) 



700 

600 

2 500 

CL 
Q. 

— 400 

S 300 

c 

m 200 - 
100 - 





Avg S.D. = 48.25 ppb 



-O— Control 
-B-0.1 mg/L 
-A-1 mg/L 
-X-5 mg/L 
-*-10 mg/L 



60 120 

Time (minutes) 



180 



240 

"Referenced to internal 
standard, chtorobenzene 



Figure 4-5. Benzene Concentration as a Function of Time and MB 

Concentration in Sunlight; (a) pH=10, 1 = 542-696 W/m 



(b) pH=7, I aVK = 665-891 W/m 



73 






500 



(a) 




— 0- 


Control 


-x- 


0.1 mg/L 




1 mg/L 


— Q- 


5 mg/L 




-10 mg/L 



60 120 180 

Time (minutes) 



240 



"Referenced to internal 
standard, chlorobenzene. 



350 




-O- Control 
-B-0.1 mg/L 
^A-1 mg/L 
-X-5 mg/L 
-X-10 mg/L 



60 120 

Time (minutes) 



180 



240 



•Referenced to internal 
standard, chkxobenzene 



(b) 

Figure 4-6. Toluene Concentration as a Function of Time and MB 

Concentration in Sunlight; (a) pH =10, I avK = 542-696 W/m 



(b) pH=7, I avg = 665-891 W/m 2 






74 



(a) 



Q. 
Q. 

<D 

c 

0) 
N 

c 
CO 




-O- Control 
-B-0.1 mg/L 
^A-1 mg/L 
^C^5 mg/L 
-3K-10 mg/L 



60 120 180 

Time (minutes) 



240 



•Referenced to internal 
standard, chlorobenzene 







§ 500 
2 400 

c 300 

a 

m 200 



100 



(b) 
Figure 4-7. 



-I 





Avg S. D. = 36.02 ppb 



-♦—Control 
-B-0.1 mg/L 
-&-1 mg/L 
-X-5 mg/L 
-X-10 mg/L 



60 120 180 

Time (minutes) 



240 

•Referenced to internal 
standard, chlorobenzene 



Benzene Concentration as a Function of Time and RB 
Concentration in Sunlight; (a) pH =10, T = 715-775 W/m 2 



(b) pH=7, I avg = 746-856 W/m 2 



(a) 



100 




75 




Avg S. D. = 57.09 ppb 



60 120 180 

Time (minutes) 



*♦— Control 
-B-0.1 mg/L 
-A-1 mg/L 
"X~5 mg/L 
^K^10 mg/L 



240 



•Referenced to internal 
standard, chlorobenzene 









600 



(b) 








60 120 180 

Time (minutes) 



— o- 


Control 




0.1 mg/L 




1 mg/L 


-* 


5 mg/L 




-10 mg/L 



240 



"Referenced to internal 
standard, chlorobenzene 



Figure 4-8. Toluene Concentration as a Function of Time and RB 

Concentration in Sunlight; (a) pH =10, I avB = 715-775 W/m 2 
(b) pH=7, I avg = 746-856 W/m 2 



avg 



76 



Table 4-9. Normalized Benzene (±0.09) and Toluene (±0.11) Concentration 
in MB Experiments 



BENZENE 


Sunlight pH 10 


Sunlight pH 7 


Dark pH 10 


Dark pH 7 


Control 














N 60 /N 


0.78 


0.96 


0.90 


1.01 




N 120 /N 


0.59 


0.86 


0.75 


0.87 


0.1 mg/L 












N 60 /N 


0.77 


0.88 


1.02 


0.83 




N 240 /N„ 


0.67 


0.80 


0.68 


0.77 


1 mg/L 














N 60 /N 


0.86 


0.85 


0.72 


0.79 




1WN 


0.71 


0.80 


0.59 


0.71 


5 mg/L 














N 60 /N 


0.87 


0.76 


0.95 


0.90 




N 240 /N„ 


0.77 


0.65 


0.65 


0.75 


10 mg/L 














N 60 /N 


0.75 


0.92 


0.98 


0.81 




N 240 /N 


0.63 


0.77 


0.74 


0.72 


TOLUENE''' 


SunlightpH 10 


SunlightpH 7 


Dark pH 10 


DwfkpH7 


Control 














N 60 /N 


0.70 


0.88 


0.85 


0.99 




N 120 /N 


0.49 


0.77 


0.68 


0.76 


0.1 mg/1 


I 












N 60 /N 


0.72 


0.80 


0.98 


0.76 




N 240 /N 


0.57 


0.57 


0.58 


0.63 


1 mg/L 














N 60 /N 


0.82 


0.77 


0.66 


0.71 




N 240 /N 


0.64 


0.67 


0.51 


0.58 


5 mg/L 














N 60 /N 


0.77 


0.72 


1.01 


0.84 




N 240 /N 


0.64 


0.54 


0.55 


0.63 


10 mg/L 














N 60 /N 


0.70 


0.85 


0.92 


0.78 




N 240 /N 


0.53 


0.62 


0.65 


0.63 



77 



Table 4-10. Normalized Benzene (±0.06) and Toluene (±0.07) Concentration 
in RB Experiments 



BENZENE 


Sunlight pH 10 


Sunlight pH 7 


Dark pH 10 


Dark pH 7 


Control 












Neo/N,, 


0.94 




0.81 


1.04 


0.95 


N 12( /N 


0.68 




0.74 


1.02 


0.86 


0.1 mg/L 












Neo/No 


0.93 




0.87 


1.00 


0.87 


N 24( /N 


0.85 




0.77 


0.71 


0.81 


1 mg/L 












Neo/No 


0.90 




0.83 


0.84 


0.91 


N 240 /N 


0.65 




0.81 


0.71 


0.78 


5 mg/L 












Neo/N,, 


0.84 




0.82 


1.00 


0.81 


N 24( /N 


0.64 




0.73 


0.81 


0.69 


10 mg/L 












Neo/No 


0.72 




0.85 


0.90 


0.95 


N 240 /N 


0.66 




0.74 


0.77 


0.75 


TOLUENE 


Sunlight pH 10 


SuniightpHf 


Dark pH 10 


DarkpH7 


Control 












Neo/No 


0.86 




0.82 


1.01 


0.94 


N I2( /N 


0.58 




0.69 


1.03 


0.81 


0.1 mg/L 












Neo/No 


0.89 




0.83 


0.99 


0.89 


N 240 /N 


0.76 




0.71 


0.65 


0.75 


1 mg/L 












Neo/N 


0.87 




0.79 


0.78 


0.89 


N 240 /N 


0.59 




0.73 


0.65 


0.71 


5 mg/L 












Neo/No 


0.78 
0.53 




0.78 


0.96 
0.69 


0.78 


N 240 /N 




0.64 


0.61 


10 mg/L 












Neo/No 


0.71 




0.82 


0.87 


0.91 


N 240 /N 


0.62 




0.65 


0.69 


0.65 



78 



(a) 




60 120 180 

Time (minutes) 



240 



* Referenced to internal 
standard, chlorobenzene 



O No MB, Sunlight 
-O-NoMB, Dark 



^^0.10 mg/L, Sunlight 
-K- 0.10 mg/L, Dark 




^ 0.60 

o 

0.40 
0.20 

0.00 






Avg S. D. = 0.04 



60 120 180 

Time (minutes) 



240 



* Referenced to internal 
standard, chkxooenzene 



-O^No MB, Sunlight 
-©—No MB, Sunlight 



0.1 mg/L, Sunlight 
■0.1 mg/L, Dark 



(b) 

Figure 4-9. Normalized Benzene Concentration in Sunlight with 0.1 mg/L 
MB, (a) pH =10, I avg = 542-696 W/m 2 (b) pH=7, 1 = 665-891 W/m 



79 



(a) 





1.00 I 
0.90 










0.80 










0.70 










0.60 








o 
o 


0.50 
0.40 
0.30 
0.20 
0.10 
On 


Avg S.D. = 0.07 










C 


) 50 100 150 
Time (minutes) 


200 

* Referenced to internal 
standard, chlorobenzene 






A 


No MB, Sunlight — Q— 0.1 mg/L, 


Sunlight 






V 












Dark 






X 


imo Mb, uarK a u.n mg/L, 







1.00 




0.90 




0.80 




0.70 




0.60 


o 
o 


0.50 
0.40 




0.30 




0.20 




0.10 



0.00 




60 120 

Time (minutes) 



180 



240 



* Referenced to internal 
standard, chlorobenzerte 



No MB, Sunlight 
-No MB, Dark 



+ 



0.1 mg/L, Sunlight 
-0.1 mg/L, Dark 



(b) 

Figure 4-10. Normalized Toluene Concentration in Sunlight with 0.1 mg/L 
MB; (a) pH =10, T = 542-696 W/m 2 (b) pH=7, I avE = 665-891 W/m 















80 



(a) 



1.20 



0.20 
0.00 




Avg S.D. = 0.28 



4- 



60 120 180 

Time (minutes) 



240 



'Referenced to internal 
standard, chlorobenzene 



-O^No MB, Sunlight 
-O— No MB, Dark 



-B— 0.1 mg/L, Sunlight 
-H — 0.1 mg/L, Dark 



o 
o 



1.00 
0.90 
0.80 
0.70 
0.60 
0.50 
0.40 
0.30 
0.20 
0.10 
0.00 




Avg S. D. = 0.05 



60 120 

Time (minutes) 



180 



240 

'Referenced to internal 
standard, chiorobenzene 



■No MB, Dark 
No MB, Dark 



-H — 0.1 mg/L, Sunlight 
-O— 0.1 mg/L, Dark 



(b) 

Figure 4-11. Normalized Benzene Concentration in Sunlight with 0.1 mg/L 
RB, (a) pH =10, 1 = 715-775 W/m 2 (b) pH=7, 1 = 746-856 W/m 2 



avg 






81 



(a) 




60 120 180 

Time (minutes) 



240 



•Referenced to internal 
standard, chlorobeneene 



No MB, Sunlight 
-No MB, Dark 



0.1 mg/L, Sunlight 
-0.1 mg/L , Dark 




240 



Time (minutes) 



'Referenced to internal 
standard, chlorobenzene 



-No MB, Sunlight 
No MB. Dark 



1 mg/L, Sunlight 
01 mg/L, Dark 



(b) 

Figure 4-12. Normalized Toluene Concentration in Sunlight with 0.1 mg/L 
RB, (a) pH =10, I avK = 715-775 W/m 2 (b) pH=7, I ave = 746-856 W/m 2 



avg 



Data Analysis bv ANOM 

Initial observation of the disinfection data for dye photosensitization 
suggested that photochemical destruction may have taken place. 
Therefore, these data were selected for additional analysis by ANOM. The 
fractional survival of colony forming units (cfu) after 5 minutes, 15 minutes 
and 30 minutes were all analyzed in this manner, for both MB and RB 

experiments. An a-level of 0.05 was used for all data presented. 

ANOM was used to examine the controlled parameters for the 
experiments, presence or absence of sunlight, pH level, and dye 



82 

concentration. The presence and absence of sunlight appeared to be the 
most significant factor in both MB and RB experiments, based upon the 
ANOM. 

Grand averages were calculated separately for the MB and RB data 
at 5, 15 and 30 minutes using fractional survival of cfu. The grand 
averages calculated for MB experiments were 0.39 (±0.14), 0.28 (±0.13) and 
0.23 (±0.13) for 5, 15 and 30 minutes, respectively. Both the grand averages 
and average standard deviations were slightly higher for the RB 
experiments with grand average values of 0.71 (±0.19), 0.61 (±0.24) and 0.47 
(±0.16), respectively, for 5, 15, and 30 minutes. The general values 
calculated for use in ANOM are given in Table 4-11. 

Table 4-11. Calculated ANOM Values for Dye Photosensitized Disinfection 



Sample Set 


Grand Average, 


X 


Avg Std Dev 


Avg Range 


SD(X) 


RB @ t=5 minutes 


0.71 




0.19 


0.46 


0.23 


RB @ t=15 minutes 


0.61 




0.24 


0.57 


0.27 


RB @ t=30 minutes 


0.47 




0.16 


0.36 


0.21 


MB @ t=5 minutes 


0.39 




0.14 


0.31 


0.20 


MB @ t=15 minutes 


0.28 




0.13 


0.31 


0.18 


MB @ t=30 minutes 


0.23 


0.13 


0.30 


0.18 



Effect of Sunlight 

The data from each sample set (5, 15 and 30 minutes) were separated 
into two subgroups, based on the absence and presence of sunlight. This 
gave an n value of 30 samples per subgroup and a k value of 2 subgroups for 
each sample set. The n and k values were used to determine the degrees of 
freedom, v, bias correction factor, d/, and , subsequently, ANOM critical 
value, H, from the bias correction factor and critical values tables (Wheeler 



83 

1990). The corresponding values were v = 33.5, d/ = 4.116, and, for an a = 

0.05, H = 1.44. These values, along with the values in Table 4-11, were used 
to determine the decision limits as shown in Equations 4-4 to 4-6. 

For each subgroup, in this case sunlight and dark, an average was 
calculated and plotted on a chart with the decision limits. The subgroup 
averages for sunlight in both the MB and RB experiments are shown in 
Table 4-12. As noted previously, a subgroup average outside of the decision 
limits indicated a parameter was statistically significant. As shown below 
the absence or presence of sunlight was found to be statistically significant 
in all cases tested for both MB (Figure 4-13) and RB (Figure 4-14) 
experiments. 



Table 4-12. Sunlight Subgroup Averages for Dye Photosensitized 
Disinfection; Values are Fractional Survival of E. coli 



MB Subgroup 


Sunlight (542 


■ 891 W/m 2 ) 




Dark 






X 


S 


R 


X 


S 


R 


t = 5 minutes 
t = 15 minutes 
t = 30 minutes 


0.282 
0.141 
0.038 


0.064 
0.069 
0.033 


0.139 
0.153 
0.075 


0.501 
0.454 
0.420 


0.212 
0.196 
0.227 


0.479 
0.461 
0.528 


RB Subgroup 


Sunl 


ight(715 


• 856 W/m 2 ) 




Dark 






X 


S 


R 


X 


S 


R 


t = 5 minutes 
t = 15 minutes 
t = 30 minutes 


0.598 
0.371 
0.132 


0.224 
0.231 
0.146 


0.518 
0.541 
0.330 


0.830 
0.850 
0.802 


0.166 
0.253 
0.165 


0.396 
0.595 
0.390 



84 



(a) 



0.55 
0.50 

0.45 



>Dark 



UDL = 0.44 



40 -I 1 Grand Av JL 

1 T 0~352 

0.35 4 



z 0.30 
0.25 
0.20 
0.15 4- 
0.10 



LDL = 0.34 



Sunlight 

(542 - 891 

W/m 2 ) 



" 



-UDLxbar 



-LDLxbar — 



■-Gavg 



-Light 



(b) 



0.50 



0.45 
0.40 
0.35 



0.25 
0.20 
0.15 
0.10 



UDL = 0.35 



■> 0.30 I J. 



LDL = 0.25 



•UDLxbar- 




Dark 



Grand Avg 
— D-2S7 - 



Sunlight 

(542 - 891 

W/m 2 ) 



-LDLxbar Gavg ♦ Light 



0.40 


UDL = 0.38 


♦ Dark 




0.35 - 




/ 




0.30 




/ 




0.25 ■ 
0.20 - 




-/-- 


Grand Avg 

0.23 


0.15 




/ 




0.10 








0.05 
00 


LDL = 0.08 


/ Sunlight 
f (542 - 891 
W/m 2 ) 





-UDLxbar- 



-LDLxbar Gavg 



"Light 



(C) 

Figure 4-13. Significance of Sunlight, Based on ANOM, in MB Experiments 
(a) 5 Minutes (b) 15 Minutes (c) 30 Minutes 



85 



(a) 



0.90 

0.80 

0.70 

0.60 
?0.50 
■0.40 

0.30 4 

0.20 

0.10 

0.00 



UDL = 0.77 »Dark 

/Sunlight 

LDL = 0.65 «f(715-856 
W/m 2 ) 



Grand Ave 

— o~7r 



-UDLxbar- 



-LDLxbar Gavg ' 



-Light 



(b) 



UDL = 0.68 



? 0.50 



0.40 
0.30 
0.20 
0.10 



LDL = 0.54 



-UDLxbar- 




Dark 



0.90 

0.80 

0.70 

Grand Av ; 



Sunlight 

(715-856 

W/m 2 ) 



-LDLxbar Gavg 



-Light 



(O 



0.90 
0.80 
0.70 
0.60 
0.50 
0.40 
0.30 
0.20 
0.10 
0.00 



UDL = 0.52 



LDL = 0.41 




Dark 



Grand Avg 



Sunlight 

(715-856 

W/m 2 ) 



-UDLxbar ■ 



-LDLxbar Gavg — ♦—Light 



Figure 4-14. Significance of Sunlight, Based on ANOM, in RB Experiments; 
(a) 5 Minutes (b) 15 Mintues (c) 30 Minutes 



86 

Effect of pH 

As was done for evaluation of the effect of sunlight, the data from 
each sample set (5, 15 and 30 minutes) were separated into two subgroups, 
based upon the pH value of 7 or 10. Since k and n were the same, and the 
same a-level was used, the values for v, d/ , and H were also the same. 

Again, these values, along with the values in Table 4-11, were used to 
determine the decision limits as shown in Equations 4-4 to 4-6. 

For each subgroup, in this case pH=7 and pH=10, an average was 
calculated and plotted on a chart with the decision limits. The subgroup 
averages for pH are shown in Table 4-13. ANOM charts are shown in 
Figures 4-15 and 4-16. 



Table 4-13. pH Subgroup Averages for Dye Photosensitized Disinfection. 
Values are Fractional Survival of E. coli. 



MB Subgroup 




pH = 


:10 






pH = 7 






X 


s 




R 


X 


s 


R 


t = 5 minutes 
t = 15 minutes 
t = 30 minutes 
RB Subgroup 


0.38 
0.31 
0.21 


0.09 
0.07 
0.10 


:,_ 


0.20 
0.15 
0.23 


0.40 
0.28 
0.25 


0.34 
0.19 
0.35 


0.76 
0.46 
0.83 




X 


S 




R 


X 


s 


R 


t = 5 minutes 
t = 15 minutes 
t = 30 minutes 


0.78 
0.69 
0.55 


0.07 
0.16 
0.12 




0.16 
0.37 
0.27 


0.65 
0.54 
0.38 


0.26 
0.32 
0.19 


0.63 

0.76 
0.45 



87 



0.50 
0.45 
0.40 
0.35 
0.30 
0.25 



-UDL = 0.44 


■; 


^XpH 7 Grand Avg 
~">CpH10" °" 39 


LDL = 0.34 



(a) 



■UDLxbar ■ 



■LDLxbar Gavg — K — pH 



(b) 



0.40 
0.38 
0.36 
0.34 
0.32 
0.30 
0.28 
0.26 
0.24 

0.22 4 

0.20 



UDL = 0.35 



\dH 10 

^CpH7 



Grand Avg 

Tr.3o- 



LDL = 0.25 



■UDLxbar- 



■LDLxbar Gavg — K — pH 



(O 



0.50 
0.45 
0.40 
0.35 
o 0.30 

1 0.25 

2 0.20 
0.15 
0.10 
0.05 
0.00 



UDL = 0.38 



JXpH 7_ _Grand Avg 

yfH10 "D.73 



- LDL = 0.08 



-UDLxbar 



-LDLxbar Gavg — X — pH 



Figure 4-15. Significance of pH, Based on ANOM, in MB Experiments; (a) 5 
Minutes (b) 15 Minutes (c) 30 Minutes 



88 



(a) 



1.00 

0.90 
0.80 
;0.70 
0.60 
0.50 
040 






UDL = 0.77 



tUh 1 ( 



\ Grand Avg g 



LDL = 0.65 



pH^f- 



-UDLxbar • 



-LDLxbar Gavg — X — pH 



(b) 



UDL = 0.68 



0.80 
0.75 
0.70 4- 
0.65 
o 0.60 -f 
\ 0.55 



0.50 
0.45 
0.40 
0.35 j 
0.30 -L 



LDL = 0.54 




Grand Aye 

0.61 



p+tT 1 - 



-UDLxbar ■ 



-LDLxbar Gavg — M — pH 



0.60 
0.50 
0.40 

o 

^,0.30 
0.20 
0.10 
000 



UDL = 0.52 


XjdH 10 







\— 


Grand Ave 


" LDL = 0.41 


VpH 7 




-■ 







-UDLxbar 



•LDLxbar Gavg — X — pH 



(0 

Figure 4-16. Significance of pH, Based on ANOM, in RB Experiments; (a) 5 
Mintues (b) 15 Minutes (c) 30 Minutes 



89 

It is clear that pH was statistically insignificant in MB experiments. 
This was inconsistent with the findings of Eisenberg et al. (1987), who 
reported a very strong correlation with pH values and more efficient MB 
inactivation at a basic pH. 

The ANOM tests were somewhat inconclusive for RB experiments. 
The data suggested that a neutral pH of 7 was slightly more effective for 

disinfection than the basic pH of 10; however, since the a-level used for 

determination of critical values was 0.05, it was possible that the signals 
were false and, therefore, not significant. 
Effect of Dye Concentration 

For evaluation of the effect of the concentration of MB and RB, the 
data from each sample set (5, 15 and 30 minutes) were separated into five 
subgroups, based upon the concentration of dye. This gave an n value of 12 
samples per subgroup and a k value of 5 subgroups for each sample set. 

The n and k values were used to determine the degrees of freedom, v, bias 

correction factor, d 2 \ and, subsequently, ANOM critical value, H, from the 
bias correction factor and critical values tables (Wheeler 1990). The 
corresponding values were v = 44.1, d/ = 3.276, and, for an a = 0.05, H = 

2.39. These values, along with the values in Table 4-11, were used to 
determine the decision limits as shown in Equations 4-4 to 4-6. 

For each subgroup an average was calculated and plotted on a chart 
with the decision limits. The subgroup averages for dye concentrations in 
both the MB and RB experiments are shown in Table 4-14. As shown in 
Figure 4-17, signals were obtained for the control reactor on the upper side, 



90 

and for 5 and 10 mg/L of MB on the lower side, indicating that the absence 
or presence of MB was significant at both 5 and 15 minutes. However, by 30 
minutes (Figure 4-17c), the presence of MB was no longer of significance, 
and disinfection in sunlight alone was just as effective. 

The presence of RB, however, in any concentration, did not appear to 
differ significantly from the absence of RB, suggesting that it neither 
enhanced nor detracted from the photolytic disinfection (Figure 4-18). 

Since MB concentration displayed some significance, each of the 
subgroup averages at 5 minutes was plotted against the control and the 
high concentration (10 mg/L) to determine the minimum significant 
concentration. These combinations allowed for the determination of 
optimum concentration range for the fastest disinfection. There were 
again two subgroups, for a k of 2, with the n value (samples per subgroup) 

remaining at 12. The corresponding table values were v = 17.8, d/ = 3.304, 
and, for an a = 0.05, H = 1.5. 



Table 4-14. Dye Concentration Subgroup Averages in Disinfection 
Experiments. Values are Fractional Survival of E. Coli. 



MB 




Ctrl 




0.1 mg/L 


1 mg/L 


5 mg/L 10 mg/L 




X 


S 


R 


X s R 


X s R 


X s R X s R 


5 

15 

30 


0.90 
0.64 
0.47 


0.23 
0.21 
0.28 


0.52 
0.48 
0.65 


0.54 0.13 0.30 
0.40 0.17 0.41 
0.36 0.20 0.48 


0.38 0.13 0.29 
0.31 0.13 0.31 
0.25 0.08 0.18 


0.10 0.14 0.31 0.04 0.06 0.13 
0.09 0.10 0.23 0.04 0.05 0.11 
0.05 0.07 0.14 0.02 0.02 0.05 


RB 




Ctrl 




0.1 mg/L 


1 mg/L 


5 mg/L 10 mg/L 




X 


S 


R 


X s R 


X S R 


X s R X s R 



5 0.82 0.18 0.43 0.68 0.25 0.58 0.66 0.24 6.56 0.73 0.16 6.38 0.70 6.15 0.34 

15 0.64 0.28 0.66 0.55 0.30 0.72 0.60 0.25 0.53 0.70 0.18 0.44 0.56 0.20 0.47 
30 0.52 0.15 0.35 0.48 0.17 0.40 0.44 0.21 0.49 0.48 0.12 0.27 0.42 0.13 0.29 



91 



(a) 



1.00 



Control 




0.40 

0.30 

020 f LDL = 0.26 

0.10 

0.00 



Grand Avg 



10 mg/L 



-UDLxbar 



■LDLxbar Gavg B MB Cone 



(b) 



0.70 
0.60 
0.50 - 



[Control 



0.40 
0.30 
0.20 



UD = 0.4 



0.10 4- LDL = 0.17 
0.00 




mg/L Grand Avg 
^ CT3U-- 



10 mg/L 



-UDLxbar- 



-LDLxbar Gavg — B MB Cone 



(C) 






0.50 
0.40 
0.30 
0.20 
0.10 
0.00 
-0.10 



-UDL = 0.47 


^Control 






DJ mg/L 




>1 mall Grand Avg 


-■ 


\ — 0~23 - 




^ a -« 10 mg/L 


LDL = 0.01 



■UDLxbar' 



-LDLxbar Gavg — B— MB Cone 



Figure 4-17. Statistical Significance of MB Concentration, Based on ANOM, 
on Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30 
Minutes 



1.00 

0.90 

0.80 

0.70 

0.60 

0.50 

0.40 +■ 

0.30 

0.20 



UDL = 0.87 


OXontrol 


UK fT 


HlLin 0fl 


^O-LJT 


fl^lmg/L 


~*-T0Trtg7r 


- LDL = 0.56 






- 







0.71 



(a) 



-UDLxbar- 



-LDLxbar Gavg 



-MB Cone 



(b) 



1.00 
0.90 
0.80 
0.70 

o 

5 0.60 

z 
0.50 

0.40 

0.30 

0.20 



UDL = 0.80 




mg/L 



LDL = 0.42 



Grand Avg 
— C.61 



■UDLxbar ■ 



-LDLxbar Gavg 



-MB Cone 



(0 



0.70 
0.60 
0.50 
: 0.40 
! 0.30 
0.20 
0.10 
0.00 




UDL = 0.61 



LDL = 0.32 



;, Grand Avg 

0-47"* 

10 mg/L 



-UDLxbar- 



-LDLxbar Gavg —a RB Cone 



Figure 4-18. Statistical Significance of RB Concentration, Based on ANOM, 
on Disinfection in Sunlight; (a) 5 Minutes (b) 15 Minutes (c) 30 
Minutes 






98 

As noted previously, a subgroup average outside of the decision limits 
indicated a parameter was statistically significant. When all of the MB 
concentrations were considered, the presence of at least 5 mg/L MB showed 
significance up to 30 minutes. By 30 minutes, the presence of MB no longer 
had an impact on the destruction of E. coli. The presence of RB was not 
significant in any instance, as was anticipated from the initial 
observations. 

In order to determine the minimum effective MB concentration, the 5 
minute subgroup averages were plotted against the control, and then, 
selectively, against each other. Every concentration showed significance 
relative to the control, suggesting that all concentrations contribute to 
photodynamic action. When examined relative to 10 mg/L, all 
concentrations except 5 mg/L showed a significant difference, suggesting 
that an increase in effectiveness occurred with increases in MB 
concentration up 5 mg/L. 




■UDLxbar- 



■LDLxbar Gavg ' 



■MB Cone 



Figure 4-19. Comparison of Disinfection Efficacy of Control and 0.1 mg/ L 
MB in Sunlight at 5 minutes, Based on ANOM 



94 



z 



0.90 
0.80 
0.70 
0.60 
0.50 
0.40 
0.30 
0.20 
0.10 
0.00 





Contror 




UDL = 0.71 










Grand Avg 


-- 




0.63 


LDL = 0.54 




\ 


- 




TD 1 mg/L 


-- 







■UDLxbar 



■LDLxbar Gavg 



■MB Cone 



Figure 4-20. Comparison of Disinfection Efficacy of Control and 1 mg/L MB 
in Sunlight at 5 minutes, Based on ANOM 



5 



0.70 

0.60 

0.50 

0.40 

0.30 4 

0.20 

0.10 

0.00 



^Control 






UDL = 0.45 \ 






\ 




Grand Avg 


_- 




0.36 


LDL = 0.28 










\ 






a 5 mg/L 



-UDLxbar 



-LDLxbar Gavg 



-MB Cone 



Figure 4-21. Comparison of Disinfection Efficacy of Control and 5 mg/L MB 
in Sunlight at 5 minutes, Based on ANOM 



95 



z 
5 



0.90 
0.80 
0.70 
0.60 
0.50 
0.40 
0.30 
0.20 
0.10 
0.00 



\ 


OTitrol— 




UDL = 0.56 






-- 




Grand Avg 






0.47 


LDL = 0.38 






-- 




D 10 mg/L 



-UDLxbar 



-LDLxbar Gavg 



■MB Cone 



Figure 4-22. Comparison of Disinfection Efficacy of Control and 10 mg/L 
MB in Sunlight at 5 minutes, Based on ANOM 



0.60 
0.50 



0.40 

I 0.30 

2 

0.20 
0.10 
0.00 



0.1 mg/L 



UDL = 0.38 



Grand Avg 
~~D^0" - 



LDL = 0.20 



10 mg/L 



■UDLxbar 



■LDLxbar Gavg 



•MB Cone 



Figure 4-23. Comparison of Disinfection Efficacy of 0.1 mg/ L and 10 mg/L 
MB in Sunlight at 5 minutes, Based on ANOM 















96 



0.40 
0.35 
0.30 
0.25 
0.20 
0.15 
0.10 
0.05 
0.00 



UDL = 0.30 


*1 mg/L 




1 Grand Avg 
_i cr21 


LDL = 0.12 


*10 mg/L 



■UDLxbaf 



-LDLxbar Gavg — X — MB Cone 



Figure 4-24. Comparison of Disinfection Efficacy of 1 mg/ L and 10 mg/L 
MB in Sunlight at 5 minutes, Based on ANOM 



0.20 
0.15 
0.10 



^ 0.05 



H 5 m 9 /L Grand Av£ 



0.00 



UDL = 0.15 



X10 



mg/L 



"oTBT" 



-0.05 | LDL = -0.02 
-0.10 



■UDLxbar- 



■LDLxbar Gavg — X — MB Cone 



Figure 4-25. Comparison of Disinfection Efficacy of 5 mg/ L and 10 mg/L 
MB in Sunlight at 5 minutes, Based on ANOM 



When the data were viewed graphically (Figure 4-26), a significant 
correlation was seen between the concentration of MB and disinfection, 
which was confirmed by linear regression. At the tested concentrations an 
increase in the MB concentration led to a direct increase in the effectiveness 
of disinfection with time. The strongest correlation was found with the MB 
concentration and ln(N t /N ). A linear fit gave an r 2 of 0.94, with p-values of 



97 

0.02 and 0.01 for the intercept and slope, respectively, for t=5 minutes 
(Figure 4-27). 

Acher and Juven (1977) reported that an increase in MB 
concentration from 0.5 to 5.0 mg/L caused an increase in the inactivation of 
coliform in both sewage water and tap water in sunlight. They also 
reported that 10 mg/L of RB was required to achieve the same disinfection 
effect as 4 mg/L MB, although no relationship of RB concentration and 
disinfection was reported. The results found in this experiment were 
consistent with those reported by Acher and Juven (1977) with regard to 
destruction of E. Coli by MB. 



1.00 a 








0.90 - 








0.80 






" 




0.70 - 
0.60 - 










5 0.50 < 






_ 




2 0.40 - 












0.30 












0.20 








^^^^ __ 




0.10 - 














00 ' 














0.00 


0.10 1.00 5.00 


10. 








mg/L Meth 


/lene Blue 







Figure 4-26. Fractional Survival of E. coli in sunlight at t=30 minutes as a 

Function of MB Concentration; Bars are One Standard Deviation 



Effect of Initial Coliform Density 

As shown in Table 4-2 the initial coliform density varied broadly 
between experiments. The variations seen across experiments were also 
present, though to a lesser extent, within each experimental set. 



98 

Analysis of the data indicated no significant correlation of initial 
coliform density with fractional survival (N t /N ) at time t for either dye. The 
typical relationship, based on the mean values from all experiments, is 
shown for both MB (Figure 4-28) and RB (Figure 4-29). 



ooo 4 


_ 050 y = -0.28x- 0.5175 
>\ R 2 = 0.94 




-1.00 


*>w 




2-1.50 

■2. 

~ -2.00 






-2.50 


• ^V. 




-3.00 


^\n 


-3 50 






0.00 2.00 4.00 6.00 8.00 10.00 


mg/L Methylene Blue 


O LN(N5/N0) Regression, ln(N5/N0) 





Figure 4-27. Least Squares Regression of Natural Logarithm of Fractional 
Survival of E. coli as a Function of MB Concentration at t=5 
Minutes (p-values for intercept and coefficient are 0.02 and 0.01, 
respectively) 



1.00 
0.90 
0.80 






D 




a 


0.70 


□ 










0.60 












0.50 


n 




D 






0.40 - 








?~* 


a 


0.30 - 








a 


0.20 - 












0.10 
0.00 


dRj 


B 

n 





a 


c 






500 


1 000 1 5( 








Initial Colony Count, cfu/L 


x 10 3 



Figure 4-28. Initial Colony Count vs. Fractional Survival of E. coli at t=60 
Minutes for MB Experiments 



■s 



83 



it 

o 

>. 
c 
o 
o 
o 



200 
000 
800 
600 
400 
200 







o 

o 



** 






— I — 

500 1000 1500 

Initial Colony Count (cfu/L x 10 3 ) 



2000 



Figure 4-29. Initial Colony Count vs. Fractional Survival of E. coli at 
t=30 Minutes in RB Experiments 



Correlation of initial coliform density with disinfection rate has not 
been reported in the literature for dye photosensitization. The indication, 
from the results of these experiments, was that no true correlation exists. 
This is consistent with the findings of Ti0 2 photocatalysis reported in this 
chapter. 
Reactor Efficacy 

After numerous iterations of reactor configurations with no evidence 
of destruction of chemical contaminants, the question of the effectiveness of 
the reactor and/or reaction process arose. Examination of the problem led 
to several possibilities for ineffectiveness of the reactor or reaction process: 

• dye concentrations were not consistent with previous work 

• reactor was not transparent to light of appropriate wavelengths; 

• dye used was not photoactive. 
























100 

Consistency with previous work 

In order to provide confidence in the reactor system, a set of 

experiments was conducted which reproduced results found in the 

literature. Eisenberg et al. (1987) were able to destroy bromacil in 

wastewater with MB in sunlight under a variety of pH conditions using 

several MB concentrations. While these experiments did not attempt to 

duplicate the work conducted by Eisenberg et al., there was a desire to 

ensure that similar results could be obtained using the photosensitization 

reactor design. Photosensitization of water containing bromacil with 10 

mg/L MB resulted in a 75% reduction, from 1448 ppb (±218) to 358 ppb 

(±48.5), after four hours of irradiation in sunlight versus a 13% reduction, 

to 1265 ppb, for the control reactor with no MB. 

Transparency of reactor. 

Disinfection of E. coli occurred in all reactors tested in the sunlight, 

but not in the reactors tested in the dark in both the MB and RB 

experiments. This disinfection occurred, albeit at different rates, both in the 

presence and absence of dye. Were the reactors not transparent to sunlight, 

there would have been no difference in disinfection between the reactors 

run in sunlight and those held in the dark chamber. 

Photoactivity of dyes 

Observation of the reactors in sunlight provided visual evidence of the 

photoactivity of the dyes. Methylene blue and, to a lesser extent rose bengal, 

began to self-destruct in sunlight. The disappearance of the dye suggested 

clearly that the dye was photoactive, as this was the behavior anticipated by 

the photoactive dye (Schlauch 1987). Indeed, the fact that the dye would 



101 

eventually react with itself was one of the features which made it attractive 

as a water treatment photochemical. 

Summary 

Of the systems tested in these experiments, photosensitized 
disinfection with methylene blue was the only process which yielded 
positive results. While disinfection did occur in the presence of rose bengal, 
it did not enhance the reaction to any degree. There were no indications at 
all that photosensitization occurred with respect to the chemical 
contaminants with either methylene blue or rose bengal. Consequently, 
with the exception of methylene blue photosensitized disinfection, these 
processes did not show promise for application. 

Initial results indicate promise for methylene blue disinfection; 
however, before the process is viable, additional, application specific, 
research is required. The positive aspects were pH and dosage of MB. 
Since pH was not a significant factor, no adjustments would be required for 
use of MB as a disinfectant. While dosage was of some importance, it 
would not require tight control. 

One drawback to the use of MB as a disinfectant for drinking water 
was the presence of color. While all of the MB disappeared from reactors at 
the lower dosages, by the end of a four hour experiment, some slight color 
was still visible at the higher dosages (5 and 10 mg/L). The color in the 
water would likely be a deterrent for use as drinking water, particularly if 
the water was clear prior to treatment. In most cultures there is an 
expectation that ingested substances be visually appealing, including 
colorless water. 



102 

Most importantly, however, in order for this process to be determined 
feasible for application, it must be tested over a much broader range of 
microbiological contaminants. Site specific testing is a must, as species 
may differ from one locale to the other. Additionally, the process would 
need to be tested for inactivation of viruses and cysts. 

While the addition of MB did increase the rate of disinfection over 
sunlight alone, the advantage may not be enough to justify the addition of a 
foreign substance into a drinking water system, no matter how benign. 

Photocatalvsis with Titanium Dioxide 

Laboratory experiments were conducted to determine the effects of 
Ti0 2 concentration and pH on the destruction of bacteria (Escherichia coli, 
Pseudomonas aeruginosa, and Serratia marcescens) and aromatic 
hydrocarbons (benzene, toluene, and xylene) under UV light. As described 
in Chapter 3 the experiments were conducted under the following 
conditions: 

• UV lamps and dark, 

• pH 4 and pH 7, 

• 0.01, 0.05 and 0.10% Ti02. 

Initially, two experimental sets were conducted, to ensure 
reproducibility of the results. A complete set of experiments were 
represented by two reactors for each of the sets of conditions highlighted 
above, for a total of 32 reactors per set. Eight reactors were run at a time, 
every two reactors containing a different concentration of Ti0 2 , with all 
other parameters the same. A third set was conducted to collect additional 



103 

chemical analysis data; however, no microbiological data were collected 
from this set. The chemical analysis results were reported from the final 
set, and the disinfection results were reported from the first two sets. 

In the first experimental set, samples were taken directly onto agar 
plates from each reactor at time intervals of 0, 15, 30, 60, 120 and 240 
minutes. Two replicates were plated from each sample for immediate 
microbiological analysis. A second sample was taken at 0, 120 and 240 
minutes directly into headspace vials, refrigerated and saved for chemical 
analysis. In the second experimental set, samples were taken from the 
reactor at time intervals of 0, 30, 60 and 120 minutes with the same 
treatment as stated above. The samples for chemical analysis were taken 
at 0, 60 and 120 minutes directly into headspace vials, refrigerated and 
saved for chemical analysis. 

The third set of experiments was conducted because complete 
destruction of all chemical components was observed in almost all of the 
second samples in each of the first two experimental sets, making trend 
detection impossible. Samples were taken at 0, 5, 15, 30 and 60 minutes and 
refrigerated immediately. 

For the experiments conducted under UV lamps, the lamp intensity 
was measured and recorded in the light chamber to be approximately 29 
W/m 2 when the chamber door was closed. The dark experiments were 
conducted in the same chamber with the lights turned off. 

Disinfection results were reported as aggregate colony forming units 
and fractional survival of total bacteriological colonies for all species 
present. Results for detoxification of aromatic hydrocarbon compounds 



104 

were reported by individual component with the exception of m-xylene and 
p-xylene. The two isomers eluted too closely for separate peak 
identification, therefore, the results were reported as one component. 

The data, as well as the impact of each of the measured and 
controlled parameters, are explored in more detail below, and results are 
compared with published data on Ti0 2 photocatalysis of BTEX and Ti0 2 
photocatalyzed disinfection. 
General Comments About Experimental Data 

The average standard deviation of the disinfection data was 12% as 
calculated from fractional survival values. Plates on which the colonies 
were not individually identifiable and those with severe contamination were 
not counted, which resulted in the loss of approximately 50% of the plates in 
a given experimental set. The difficulties encountered in microbiological 
analysis that resulted in such a high loss rate and large standard deviation 
were attributed to three factors: 1) use of mixed cultures, 2) extremely high 
initial colony densities, and 3) inexperience of the experimenter in 
microbiological techniques. 

In the first experimental set, very few values were obtained from the 
intermediate samples at 15, 30 and 60 minutes. The colony densities were 
much too high for differentiation of the data. 

The average standard deviations of the detoxification data ranged 
from 6-9% of the average values, with o-Xylene having the highest. No 
sample loss occurred for detoxification. Chemical samples were analyzed 
within approximately two weeks of the experiment. 



105 

Statistical Treatment of the Data 

The data were treated as outlined previously in the section on dye 
photosensitization. No specific adjustments were required for the Ti0 2 
disinfection data with the exception of normalizing negative percentages of 
destruction to zero. There were two samples in chemical data thought to be 
outliers; however, since only two replicates existed, outlier detection was 
not possible. 
Presentation of Results and Identification of General Trends 

Ti0 2 photocatalysis was effective for simultaneous detoxification of 
aromatic hydrocarbons and disinfection of the mixed bacterial species 
tested over a range of conditions. The most destruction of both 
bacteriological and chemical contaminants occurred in the presence of U V 
light with 0.01% Ti0 2 ; however, disinfection seemed to be more effective at a 
pH of 4, and detoxification appeared to fare better at pH 7. 

Complete disinfection was achieved in one hour with 0.01% Ti0 2 at 
pH 4. Complete disinfection within one hour was not observed in any other 
reactor, where photocatalytic destruction of cfu ranged from 78% with 
0.01% Ti0 2 at pH 7, to 92% observed with both 0.05% at pH 4 (Figure 4-30a) 
and 0.10% Ti0 2 at pH 7 (Figure 4-30b). Complete disinfection was achieved 
by four hours with both 0.01% and 0.05% Ti0 2 at pH 7. 

Less than 60% reduction of cfu was attained in the control reactors by 
four hours of irradiation under the UV lamps, and no persistent 
destruction was observed in the dark reactors either with or without Ti0 2 . 
The data are presented as mean fractional survival of bacteria in Table 4-15. 



106 



(a) 




100 

Time (minutes) 



200 



Ti0 2 Conc. 

-6- 0.00% 
-Q- 0.01 % 
-A- 0.05% 
-X-0.10% 



1.60 



(b) 




0.00 J 



100 200 

Time (minutes) 



Tip; Cone. 



^-0.00% 
Q-0.01% 
A- 0.05% 
0.10% 



Figure 4-30. Ti0 2 Photocatalytic Disinfection in UV Light (29 W/m 2 ); Error 
Bars are One Standard Deviation; (a) pH = 4 (b) pH = 7 



The presence of Ti0 2 in reactors irradiated under ultraviolet lamps 
resulted in some destruction of all of the aromatic hydrocarbons tested at all 
concentrations. Photocatalytic destruction of all of the components to below 
the detectable limits was observed in one reactor, reactor 4, by 60 minutes. 
This reactor contained 0.01% Ti0 2 and water adjusted to a pH of 7. Figure 
4-31 is a graphical representation of this reactor and its redundant reactor 
(reactor 3), which was treated with the same conditions. 

An examination of Table 4-16 shows that photocatalytic detoxification 
took place under all conditions; however, by 60 minutes, only 50% 



107 

destruction of benzene was seen with 0.10% Ti0 2 at pH=4 and only 30% at 
pH=7 (Figure 4-32). These values are fairly consistent for all of the 
components as shown in Figures 4-33 and 4-34. Virtually no destruction of 
any of the components in the absence of Ti0 2 or in the absence of light was 
observed. 



Table 4-15. 


Mean Fractional Survival of Bacteria in 


Ti0 2 Experiments 






UV Light pH 4 


UV Light pH 7 


Dark pH 4 


Dark pH 7 


Control 


Mean 


Std Dev 


Mean 


Std Dev 


Mean 


Std Dev 


Mean Std Dev 


N 15 /N 


- 


- 


- 


- 


0.63 


0.00 


- 


- 


N 30 /N 


- 


- 


1.48 


0.08 


0.56 


0.24 


0.77 


0.20 


N 60 /N 


- 


- 


1.15 


0.10 


0.41 


0.25 


0.77 


0.08 


N 120 /N 


0.62 


0.18 


0.89 


0.07 


0.95 


0.29 


0.88 


0.03 


N 240 /N 


0.42 


0.25 


0.77 


0.03 


1.51 


1.25 


1.14 


0.17 


0.01% Ti0 2 


















N 15 /N 


0.33 


0.00 


- 


- 


- 


- 


. 


- 


N 30 /N 


0.05 


0.00 


- 


- 


0.36 


0.08 


0.88 


0.00 


N 60 /N„ 


0.00 


0.00 


0.21 


0.08 


0.29 


0.09 


0.74 


0.00 


N 120 /N 


0.00 


0.00 


0.06 


0.02 


1.06 


0.24 


0.85 


0.11 


N 240 /N 


0.00 


0.00 


0.00 


0.00 


2.15 


0.02 


1.88 


0.15 


0.05% Ti0 2 


















N 15 /N 


- 


- 


. 


. 




- 


- 


. 


N 30 /N 


0.26 


0.03 


0.59 


0.11 


0.59 


0.12 


0.62 


0.05 


N 6 „/N 


0.08 


0.01 


0.22 


0.01 


0.61 


0.01 


0.98 


0.32 


N 120 /N 


0.03 


0.00 


0.11 


0.04 


0.81 


0.08 


1.09 


0.47 


N 240 /N 


0.09 


0.08 


0.00 


0.00 


1.04 


0.17 


1.63 


0.33 


0.10% Ti0 2 


















N 15 /N 


- 


- 


- 


- 


- 


- 


- 


. 


N 30 /N 


- 


- 


0.18 


0.08 


0.78 


0.05 


0.45 


0.02 


N 60 /N 


0.18 


0.06 


0.08 


0.02 


1.22 


0.29 


0.49 


0.05 


N 120 /N 


0.23 


0.16 


0.07 


0.04 


0.99 


0.31 


1.11 


0.24 


N 240 /N 


0.12 


0.13 


0.09 


0.11 


1.21 


0.29 


1.26 


0.08 



108 



Table 4-16 


. Mean Concentration of BTEX (ppb) in Ti0 2 Experiments 






1 






BENZENE 










UV yght P H 4 


UV Light 


Dark pH 4 


Dark pH 7 


0.00% TiO, 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


765 


7 


924 


8 


922 


72 


935 


17 


5min 


813 


46 


895 


26 


1008 


90 


1019 


25 


15 min 


825 


22 


956 


41 


891 


14 


1029 


23 


30min 


769 


38 


901 


16 


828 


6 


1004 





60 min 


372 


355 


907 


36 


882 


22 


1068 


69 


0.01% TiO, 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


753 


36 


957 


6 


860 


68 


1009 


19 


5 min 


466 


84 


264 


24 


853 


2 


1069 


14 


15 min 


250 


47 


78 


8 


581 


323 


1052 


21 


30 min 


63 


20 


23 


3 


727 


10 


1016 


1 


60 min 


5 


1 


1 





754 


72 


1010 


68 


0.05% TiO, 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


867 


35 


967 


14 


865 


6 


1042 


39 


5 min 


706 


23 


707 


206 


863 


10 


1070 


27 


15 min 


488 


35 


626 


174 


838 


84 


1110 


27 


30 min 


267 


102 


448 


122 


689 


60 


1088 


1 


60 min 


187 


69 


255 


69 


812 


48 


1075 


1 


0.10% TiO, 


I AVg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


853 


8 


840 


14 


876 


17 


976 


108 


5 min 


790 


71 


902 


27 


901 


9 


985 


83 


15 min 


706 


49 


797 


14 


873 


12 


958 


45 


30 min 


629 


10 


661 


30 


756 


10 


1005 


53 


60 min 


521 


33 


602 


11 842 


10 

NMMMMMMOMMMMM 


988 


79 














UV Light pH 4 


UV Light pH 7 


Dark 


P H4 


Dark 


P H7 


0.00% Ti0 3 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


478 


2 


484 


13 


738 


67 


685 


20 


5 min 


503 


14 


491 


24 


848 


60 


745 


35 


15 min 


512 


9 


526 


18 


758 


20 


768 


9 


30 min 


509 


13 


518 


35 


700 


8 


746 


5 


60 min 


263 


252 


523 


16 


740 


3 


772 


54 


0.01% Ti0 2 ; 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


493 


22 


499 


7 


768 


65 


754 


20 


5 min 


302 


56 


130 


10 


757 





810 


5 


15 min 


153 


31 


32 


3 


522 


310 


775 


2 


30 min 


35 


13 


7 


1 


653 


15 


768 


19 


60 min 








1 





653 


58 


760 


50 


0.05% TiO, 


Avg 


Std Dev 


Avg 


Std Dev 

17"" 


Avg 
759 


Std Dev 
7 


Avg 
765 


Std Dev 


Omin 


519 


22 


522 


39 


5 min 


459 


21 


378 


103 


771 


23 


782 


27 


15 min 


309 


38 


339 


92 


748 


88 


828 


8 


30 min 


170 


72 


249 


53 


571 


90 


813 


1 


60 min 


119 


47 


136 


42 


733 


54 


808 


27 


0.10% TiO, 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


562 


11 


458 


1 


774 


11 


767 


86 


5 min 


539 


57 


496 


1 


792 


23 


764 


52 


15 min 


471 


34 


424 


8 


770 


9 


750 


59 


30 min 


410 


17 


358 


13 


674 


4 


768 


48 


60 min 


327 


30 


315 


1 


750 


10 


756 


65 



109 



Table 4-16 


-continued. 

-.-.-.-.-.-.-.-.-.-.-.-.-.•.-.-.-.■.-.-.-:-.%--.-;-.->.w.-.^ 


M4P-XYLENE 


-.•.-.-.-.-.-.-.-.-.-.-.-.-.-.-.•.■.-.-.-.-.-.-.- 


— — ■-." 






UV Light pH 4 


UV Light P H 7 


Dark 


pH4 


Dark 


pH7 


0.00% TiO, 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


201 


1 


318 


15 


444 


36 


454 


7 


5min 


204 


6 


287 


47 


514 


38 


498 


22 


15 min 


217 


7 


308 


53 


466 


2 


511 


18 


30min 


230 


8 


315 


75 


429 


9 


487 


14 


60 min 


130 


129 


311 


56 


437 





519 


8 


0.01% TiO., 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


! 192 


7 


233 


1 


484 


46 


497 


10 


5 min 


129 


33 


56 


3 


475 





532 


8 


15 min 


66 


14 


11 


1 


317 


192 


506 


11 


30 min 


11 


4 


1 





408 


3 


505 


5 


60 min 


1 





1 





438 


33 


501 


32 


0.05% Ti0 2 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


206 


13 


246 


10 


497 


3 


534 


29 


5 min 


194 


2 


186 


44 


495 


12 


542 


18 


15 min 


126 


29 


168 


36 


495 


49 


575 


4 


30 min 


68 


36 


114 


14 


341 


62 


559 


3 


60 min 


47 


23 


65 


20 


459 


44 


556 


1 


0.10% TiO, 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


233 


3 


204 


7 


495 


9 


529 


66 


5 min 


220 


25 


221 


1 


518 


9 


537 


40 


15 min 


191 


18 


196 


4 


498 


15 


533 


36 


30 min 


161 


9 


157 


7 


414 


15 


543 


54 


60 min 


125 


16 


136 


1 


467 





536 


34 


wX^-x*x-x-x-x-x-x-x-x-x-:-:-x-:- 






■■»■■■ »■»■■■■..« 


■»-■■» »"><»> 


O-XYLENE 


iMHWOMMMt x ■:-:■:■:-:-:■:• : 


^,:, K ,,:.,:,:, 


■*■—■» 


.„.,.,...,.........,....„...,...„.„.,.. 


UV Light pH 4 


UV Light 


Dark pH 4 


Dark 


pH7 


0.00% Ti0 2 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


52 


1 


107 


5 


145 


20 


147 


4 


5 min 


54 


3 


86 


24 


178 


18 


165 


12 


15 min 


60 


1 


97 


27 


157 


1 


169 


8 


30 min 


67 


4 


100 


35 


142 


3 


164 


2 


60 min 


40 


39 


98 


29 


148 


2 


178 


5 


0.01% Ti0 2 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


49 


2 


62 


3 


166 


18 


164 


6 


5 min 


45 


12 


11 





172 





181 


2 


15 min 


18 


4 


1 





106 


79 


174 


3 


30 min 


1 





1 





153 


10 


171 


2 


60 min 


1 





1 


1 


161 


1 


169 


13 


0.05% TiO, : 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


51 


8 


66 


6 


170 


2 


181 


12 


5 min 


53 


9 


53 


6 


174 


6 


186 


6 


15 min 


29 


24 


48 


2 


175 


17 


197 


4 


30 min 


17 


16 


27 


9 


119 


17 


191 


2 


60 min 


9 


8 


25 


2 


159 


17 


191 


1 


0.10% TiO, 1 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Avg 


Std Dev 


Omin 


60 


1 


52 


3 


170 


2 


177 


27 


5 min 


57 


9 


58 


1 


175 


5 


184 


18 


15 min 


43 


6 


47 


2 


173 


4 


180 


17 


30 min 


33 


3 


31 


1 


145 





186 


19 


60 min 


16 


6 


23 





164 


2 


183 


18 


l ..... B . M .. WWM .„,„.,J 


WMHMMMOMCMMWMM 


BflMMMMaWMttMOCOOft 


:*x.>x-:w>:*%v-x-:v.:-:.x-x-'-x 




•X-X-X-X*X.Xs-X-X-X^*X*XXvO:-X-X-X-X-X-X.X-X<vW 



110 



o 


c 
I 




20 40 

Time (minutes) 



60 



Reactor 3 — ■— Reactor 4 



Figure 4-31. Destruction of Benzene in Reactors 3 and 4 as a Function of 

Time; Reactors Contained 0.01% Ti0 2 and were Irradiated for 
60 minutes under UV Lamps (29 W/m 2 ) 



o 




(a) 




Ti0 2 Cone. 



Control 
0.01% 
0.05% 
0.10% 



20 40 

Time (minutes) 




TiOj Cone. 



Control 
.01% 
.05% 
.10% 



(b) 



20 40 

Time (minutes) 



Figure 4-32. Benzene Concentration in UV Light (29 W/m 2 ) as a Function 
of Time and Ti0 2 Concentration; Error Bars are One Standard 
Deviation, (a) pH =4, (b) pH = 7 



Ill 



600 




Ti0 2 Cone. 



» Control 


-0—0.01% 


-fc-0.05% 


-K-0.10% 



(a) 



20 40 

Time (minutes) 










Ti0 2 Cone. 



Control 
-0.01% 
-0.05% 
-0.10% 



(b) 



20 40 

Time (minutes) 



Figure 4-33. Toluene Concentration in UV Light (29 W/m 2 ) as a Function of 
Time and Ti0 2 Concentration; Error Bars are One Standard 
Deviation, (a) pH =4, (b) pH = 7 



Initial observation of both the disinfection and detoxification data for 
Ti0 2 photocatalysis suggested that the process displayed some efficacy. 
Therefore, these data were selected for additional analysis by ANOM. For 
disinfection the fractional survival of colony forming units after 120 
minutes were selected. The normalized concentrations of benzene and 
toluene after 30 and 60 minutes were used for the detoxification ANOM. An 



a-level of 0.05 was selected for all of the data presented. 



112 



(a) 




20 40 

Time (minutes) 



Ti0 2 Cone. 



—&- Control 


-o-0.01% 


-A-0.05% 


-tt-0.10% 



(b) 



- 400 
n 

S 350 _ 

§ 300 



sLT^, 



5 250; -J J- 

200 



e 

150 4 

a 

| 100 

X 50 

4 

1 o 




20 40 

Time (minutes) 



Ti0 2 Cone 


—$- Control 


-a— 0.01% 


-A-0.05% 


-X-0.10% 



Figure 4-34. m&p Xylene Concentration in UV Light (29 W/m 2 ) as a 

Function of Time and Ti0 2 Concentration; Error Bars are One 
Standard Deviation, (a) pH =4, (b) pH = 7 



Data Analysis bv ANOM 

ANOM was used to examine the controlled parameters for the 
experiments, presence or absence of TJV light, pH level and Ti0 2 
concentration. Based upon the ANOM, the presence and absence of light 
and the concentration of both were deemed significant factors for both 
disinfection and detoxification. 

The grand average calculated for bacteria, as fractional survival, 
was 0.66 (±0.20). The grand averages calculated for benzene were 0.75 



113 

(±0.05) and 0.70 (±0.08) for 30 and 60 minutes, respectively. The respective 
values for toluene for 30 and 60 minutes were 0.76 (± 0.06) and 0.71 (±0.08). 
The general values calculated for use in ANOM are given in Table 4-17. 



Table 4-17. Calculated ANOM Values for Ti0 2 Photocatalysis 





Grand Average, X 


Avg Std Dev 


Avg Range 


Estimated 

SD(X) 


Bacteria @ t-120 min 


0.66 


0.20 


0.40 


0.28 


Benzene @ t= 30 min 


0.75 


0.05 


0.09 


0.04 


Benzene @ t= 60 min 


0.70 


0.08 


0.15 


0.09 


Toluene @ t=30 min 


0.76 


0.06 


0.11 


0.05 


Toluene @t=60 min 


0.71 


0.08 


0.17 


0.10 


Effect of Lipht 











UV light was measured in the lab experiments to be approximately 
29 W/m 2 , a value slightly less than the measured values of UV light 
available on a clear day. Therefore, the data gathered in the laboratory 
experiments under UV light can be extrapolated to sunlight. Patel (1993) 
and Wei et al. (1994) reported disinfection efficacy in sunlight to be greater 
than in UV light. 

The data from each of the sample sets were separated into two 
subgroups based upon the absence and presence of light. This gave an n 
value of 16 samples per subgroup and a k value of 2 subgroups for each 
sample set. The n and k values were used to determine the degrees of 
freedom, v, bias correction factor, d 2 \ and, subsequently, the ANOM critical 
value, H, from the bias correction factor and critical values tables (Wheeler 
1990). The corresponding values were v = 22.5, d,* = 3.571, and, for an a = 



114 

0.05, H = 1.47. These values, along with the values in Table 4-17, were used 
to determine the decision limits using Equations 4-4 to 4-6. 

For each subgroup, in this case UV light and dark, an average was 
calculated and plotted on a chart with the decision limits. The subgroup 
averages are shown in Table 4-18. As noted previously, a subgroup average 
outside of the decision limits indicated a parameter was statistically 
significant. As shown below the absence or presence of light was found to 
be statistically significant for both disinfection and detoxification. 



Table 4-18. UV Light Subgroup Averages for Ti0 2 Photocatalysis. Values 
are Fractional Survival of Bacteria and Normalized Chemical 
Concentration. 



Subgroup 




UV 


'Light "(&W3fi 


„_„„:::,. 


->x->r-:-:-:v-x-:-:-:-:-:-:-:-:->:-:-:-:-:-:-> 

Dark 


— "— — 




X 




s 


R 


X 


S 


R 


Bacteria @ t=120 min 


0.36 




0.12 


0.24 


0.96 


0.28 


0.57 


Benzene @ t = 30 min 


0.55 




0.05 


0.09 


0.95 


0.05 


0.10 


Benzene @ t = 60 min 


0.41 




0.09 


0.19 


0.99 


0.06 


0.12 


Toluene @ t= 30 min 


0.57 




0.05 


0.10 


0.95 


0.06 


0.13 


Toluene @ t= 60 min 


0.42 




0.09 


0.09 


0.99 


0.07 


0.15 



As demonstrated by the ANOM chart (Figure 4-35), the presence of 
UV light had an appreciable impact on disinfection. This relationship is 
shown graphically in Figure 4-38. 

As shown in Table 4-15, there was some destruction of bacteria in the 
presence of light and the absence of Ti0 2 , with N 24O /N values of 0.42 (±0.25) 

and 0.77 (±0.03) for pH 4 and pH 7, respectively. This was not unexpected, 
as the bactericidal effects of both UV light (Oliver and Carey 1976; Severin 
et al. 1983; Wolfe 1990) and sunlight (Acra et al. 1990; Fujioka and 






115 

Narikawa 1982; Gameson and Saxon 1967) in aqueous systems have been 
demonstrated. 




Grand Avg 
■0-3C-- 



UV Light 



-UDLxbar 



-LDLxbar Gavg » Light 



Figure 4-35. Significance of UV Light (29 W/m 2 ), Based on ANOM, on 
Bacteria in Ti0 2 Experiments at 120 Minutes 



(a) 



0.95 
0.90 
0.85 
0.80 
O 0.75 
J 0.70 
0.65 
0.60 
0.55 
0.50 



UDL = 0.77 


- •Bark— 


n,rand Avn 






/ 




LDL = 0.73 


♦ UV Light 





-UDLxbar 



-LDLxbar Gavg ♦ Light 



(b) 



1.00 
0.90 
0.80 
J 0.70 
O 0.60 
0.50 
0.40 
0.30 



- 


• Dark 




UDL = 0.77 






1 ' ' / <jiaiiu nvy 




T 


trrr 


LDL = 0.66 


/ 






♦ UV Light 





-UDLxbar' 



-LDLxbar Gavg 



"Light 



Figure 4-36. Significance of UV Light (29 W/m 2 ), Based on ANOM, on 
Benzene in Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 



116 



1.00 

0.95 

0.90 

0.85 

= 0.80 

§0.75 

" 0.70 

0.65 

0.60 

0.55 

0.50 



UDL = 0.78 


• Dark 




_ ' " — 






trro 


.. LDL = 0.73 


• UV Light 





-UDLxbar ■ 



-LDLxbar Gavg — •— Light 



1.00 
0.90 
0.80 

cj0.70 

a o.6o 

0.50 

0.40 
0.30 



UDL = 0.77 


f Dark — 










trn 


LDL = 0.66 


# UV Light 





-UDLxbar 



-LDLxbar Gavg 



Figure 4-37. Significance of UV Light (29 W/m 2 ), Based on ANOM, on 
Toluene in Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 



0.70 




>t=2 hrs 
lt=4 hrs 



UV Light 



Dark 



Figure 4-38. Effect of UV Light (29 W/m 2 ) on Fractional Survival of Bacteria 
in All Reactors in Ti0 2 Experiments; Bars are One Standard 
Deviation 



117 

Effect of pH 

As was done for evaluation of the effect of sunlight the data from each 
sample set were separated into two subgroups, based upon the pH value of 7 

or 10. Since k and n were the same, and the same a-level was used, the 

values for v, d 2 * , and H were also the same. Again these values, along with 

the values in Table 4-17, were used to determine the decision limits using 
Equations 4-4 to 4-6. 

For each subgroup, in this case pH = 4 and pH = 7, an average was 
calculated and plotted on a chart with the decision limits. The subgroup 
averages for pH are shown in Table 4-19 and the ANOM charts are shown 
in Figures 4-39 to 4-41. 



Table 4-19. pH Subgroup Averages for Ti0 2 Photocatalysis. Values are 
Fractional Survival of Bacteria and Normalized Chemical Concentration 



Subgroup 








pH = 4 






pH = 7 










X 


S 


R 


X 


s 


R 


Bacteria @ t= 


=120 min 


0.61 


0.17 


0.35 


0.71 


0.23 


0.46 


Benzene @ t= 


=30 


min 


0.69 


0.06 


0.11 


0.80 


0.04 


0.08 


Benzene @ t= 


=60 


min 


0.63 


0.11 


0.22 


0.77 


0.05 


0.09 


Toluene @ t= 


:30 


min 


0.70 


0.06 


0.13 


0.82 


0.05 


0.10 


Toluene @ t= 


:60 


min 


0.65 


0.12 


0.24 


0.78 


0.04 


0.09 






iMMMMMHMtt 


.-.-.-.-.-.-.-.-.-.-.-.-.-.-.■.-.-.-.•.■.-.■.-.-.■.-.-.■. 


lOOMMMMMMWHMC 


w.\^w.w.w.-.w.-.w.w.w.w. 


MMMMMMMMMMOM 


-.-.-.-.-.-.-.-.■.•.■.■.-.-.-.-.-.-.-.-.-.-.-.-.-.-.•.-.-. 


■.-.-.-.-.-.-.-:-.-.-.-.-:-.-.-.-:-.-:-.-.-:-.-.-:v.-.-.- 





















118 



0.80 
0.75 ■ 
0.70 
1 0.65 - 
0.60 - 
0.55 
0.50 








UDL = 0.77 






>pH = 7 
/ Grand Avg 


^pH = 4 


LDL = 0.73 












■ r^i i ^ 













Figure 4-39. Significance of pH, Based on ANOM, to Bacteria Destruction in 
Ti0 2 Experiments at 120 Minutes 



ANOM demonstrated that, at the levels tested, pH had no significant 
effect on the destruction rate of the mixed bacteria species, E. coli, 
Pseudomonas aeruginosa, and Serratia marcescens. These findings are 
consistent with the findings of Block et al. (1997), who studied the effect of 
pH on the inactivation of Serratia marcescens and reported that acidic and 
neutral pH values, from 3.5 - 7, had no perceptible impact on disinfection 
efficacy. 

Examination of the charts above suggested that ANOM tests were 
somewhat inconclusive for detoxification. The data suggested that pH 
could be statistically significant; however, the proximity of subgroup 
averages, particularly at 60 minutes, to the decision limits indicated a need 

for caution. With an a-level of 0.05 values close to the decision limits were 

possibly false signals. 

The acid pH of 4 appeared to be slightly more effective than the 
neutral pH of 7. As shown above there was a slight difference between the 
mean normalized concentrations of BTEX components after 30 minutes and 






119 

60 minutes. While the significance of this was not conclusive, the data 
were consistent with values reported by (Kawaguchi and Furuya 1990), who 
found that 3.5 was an optimum pH for the Ti0 2 photocatalyzed degradation 
of chlorobenzene. 



(a) 



0.85 
0.80 
0.75 



J 0.70 
o 0.65 ■- 
0.60 

0.55 
0.50 



— U ---I 7 ^zzzz 7 —9i°£**j. 



■UDLxbar' 



-LDLxbar Gavg — ■ 4 — Light 



0.80 
0.75 
0.70 
^0.65 



c3 



0.60 
0.55 
0.50 



UDL = 0.75 


^pH = 7 




/ Grand Avg 




r 


XTA3 


LDL = 0.65 


^pH = 4 





■UDLxbar ■ 



■LDLxbar Gavg » Light 



(b) 

Figure 4-40. Significance of pH, Based on ANOM, to Benzene Destruction 
in Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 



The concentration of Ti0 2 appeared to have a significant impact on 
disinfection. In order to clarify the meaning of the differences seen with 
Ti0 2 concentration, ANOM tests were performed for bacteria at 120 
minutes, and benzene and toluene at 30 and 60 minutes. The data were 
divided into four subgroups based upon the concentration of Ti0 2 . This gave 
an n value of 8 samples per subgroup and a k value of 4 subgroups for each 



120 

sample set. The n and k values were used to determine v, d/, and H from 
the appropriate tables (Wheeler 1990). The corresponding values were v = 

24.4, d/ = 2.876, and, for an a = 0.05, H= 2.29. These values, along with the 

values from Table 4-17, were used to determine the decision limits using 
Equations 4-4 to 4-6. 



(a) 



0.85 
0.80 
0.75 
O 070 
O 0.65 -■ 
0.60 
0.55 
0.50 



UDL = 0.78 >PH = 7 

LDL = 0.73 ^h = 4 



Gro n d Av g 
TT7S- 



■UDLxbaf 



■LDLxbar Gavg ♦ Light 



o 

O 



0.80 
0.75 
0.70 
0.65 
0.60 
0.55 
0.50 



UDL = 0.77 


#PH = 7 




/ Grand Avg 




I 


urrr T 


LDL = 0.66 


• pH = 4 





-UDLxbar- 



-LDLxbar Gavg ♦ Light 



(b) 

Figure 4-41. Significance of pH, Based on ANOM, to Toluene Destruction in 
Ti0 2 Experiments (a) 30 Minutes (b) 60 Minutes 



Effect of TiO o Concentration 

For each subgroup an average was calculated and plotted on a chart 
with the decision limits. The calculated subgroup averages are shown in 
Table 4-20 and the ANOM charts are shown in Figures 4-42 to 4-44. 



121 



Table 4-20. Ti0 2 Concentration Subgroup Averages for Disinfection. Values 
are Fractional Survival of Bacteria and Normalized Chemical 
Concentration 



Subgroup 



Control 0.01% TiO ? 
X s R X s R 



0.05% Ti0 9 



0.10% TiO, 



R 



R 



Bacteria @ 
t=120 min 
Benzene @ 
t=30 min 
Benzene @ 
t=60 min 
Toluene @ 
t=30 min 
Toluene @ 
t=60 min 



0.93 0.10 0.21 0.48 0.11 0.23 0.36 0.09 0.18 0.71 0.44 0.89 

0.99 0.04 0.07 0.49 0.03 0.06 0.57 0.11 0.22 0.86 0.03 0.06 

0.89 0.16 0.31 0.48 0.06 0.12 0.45 0.07 0.14 0.83 0.03 0.06 

1.05 0.05 0.10 0.49 0.04 0.59 0.04 0.08 0.59 0.10 0.85 0.10 

0.09 0.17 0.33 0.45 0.06 0.12 0.45 0.09 0.17 0.81 0.02 0.05 



1.00 

0.90 

0.80 

0.70 

o 0.60 

>0.50 

2 0.40 

0.30 

0.20 

0.10 

0.00 



UDL = 0.89 n No TiO 



LDL = 0.43 




0.10% Grand Ave 
TJ.6B - 



0.05% 



-UDLxbar 



Gavg 



-LDLxbar 
-Ti02 Cone 



Figure 4-42. Significance of Ti0 2 Concentration, Based on ANOM, on 
Bacteria in Photocatalysis Experiments at 120 Minutes 



Since Ti0 2 concentration displayed some significance for both 
disinfection and detoxification, the subgroup averages were plotted against 
the control and the two concentrations which were closest together against 
each other to determine the minimum significant concentration. These 
combinations allowed for the determination of the optimum concentration 
range for the fastest destruction. There were again two subgroups, for a k 
of 2, with the n value (samples per subgroup) remaining at 8. The 



corresponding table values were v = 17.8, d 2 * = 3.304, and, for an a = 0.05, H 
= 1.54. 



(a) 



1 nr\ 








P No Ti0 2 




0.90 


\ 




0.80 


UDL = oW P0.10% 




_\ / Grand Avg 


O 

"ft 0.70 - 

o 


\ / ° /b 




LDL = 0.7o\ / 




0.60 - 


\ JlO.05% 




0.50 


cr{foi% 




n An 


























Gavg — — Ti02 Cone 















(b) 



0.90 

0.85 

0.80 

0.75 

o 0.70 
O 
~S 0.65 

0.60 

0.55 

0.50 

0.45 

0.40 



"No Ti0 2 



UDL = 



LDL = 0.60 




0.10% 



Grand Avg 
■-TJ.70 - * 



0.05% 



■UDLxbar 



Gavg 



■LDLxbar 
-Ti02 Cone 



Figure 4-43. Significance of Ti0 2 Concentration, Based on ANOM, on 

Benzene in Photocatalysis Experiments; (a) 30 Minutes (b) 60 
Minutes 















(a) 



(b) 



123 



1.10 

1.00 

0.90 

(3 0.80 

O 0.70 



0.60 
0.50 ■■ 
0.40 



No TiO 



UDL 



LDL = 0.7 




0.10% 

GrancTEvc 

-y tr.7B - 



-UDLxbar 



Gavg 



-LDLxbar 
-Ti02 Cone 



1.00 
0.90 
0.80 

o 

o 

"S 0.70 
o 

0.60 
0.50 

0.40 



UDL = 



No TiOz 
).83 



LDL = 0.59 




1 0% 



Grand Ave 
— TJ.7T 



0.05% 



-UDLxbar 



Gavg 



-LDLxbar 
-Ti02 Cone 



Figure 4-44. Significance of Ti0 2 Concentration, Based on ANOM, on 

Toluene in Photocatalysis Experiments; (a) 30 Minutes (b) 60 
Minutes 



Examination of the ANOM charts (Figures 4-45 to 4-52) indicated that 
while there was no significant difference between 0.01% Ti0 2 and 0.05% 
Ti0 2 for either disinfection or detoxification, both concentrations were 
more effective than 0.10% and no Ti0 2 . This was consistent with the initial 
trends observed wherein 0.01% was observed to be the most effective 
concentration. 



124 



1 nn 






0.90 - 
0.80 

o 

% 0.70 - 

Z 
0.60 

0.50 

n 4fi 


q No Ti0 2 
UDL = 0.86 \ 




\ Grand Ave 


LDL = 0.55 \ 

□ 0.01% 


















Gavg — D — Ti02 Cone 













Figure 4-45. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic 
Disinfection at 120 Minutes, Based on ANOM 



1.00 



0.90 
0.80 

o 

1*0.70 
0.60 
0.50 4 
0.40 



UDL = 0.88 


Q No Ti0 2 









Grand Ave 


LDL = 0.57 


D 0.05% 





-UDLxbar 



Gavg 



■LDLxbar 
-Ti02 Cone 



Figure 4-46. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic 
Disinfection at 120 Minutes, Based on ANOM 



125 



1.00 

0.95 

0.90 4 

O 0.85 

% 0.80 

Z 0.75 

0.70 

0.65 

0.60 



UDL = 0.97 






Grand Ave 




D0.10% 


0.82 


LDL = 0.67 



■UDLxbar 



Gavg 



-LDLxbar 
-Ti02 Cone 



Figure 4-47. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic 
Disinfection at 120 Minutes, Based on ANOM 



n 70 


UDL = 0.65 




0.60 








0.50 


wnn# JUB *- -Tm- q 




£ 0.40 
2 0.30 






' LDL = 0.35 


0.20 






0.10 






O 00 
























■- uuLXDar LULxoar 
Gavg — □ — Ti02 Cone 















Figure 4-48. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic 
Disinfection at 120 Minutes, Based on ANOM 



126 



n on 










Q No Ti0 2 






0.80 

0.70 

0.60 

O 0.50 - 

O 0.40 - 


UDL = 0.76 \ 






V 


Grand Ave 
TJ.58 - " 


LDL = 0.61 \ 

D0.01% 












0.30 








0.20 








0.10 








n nn - 
























-LDLxbar 








Gavg — D — 


-Ti02 Cone 

















Figure 4-49. Comparison of Control vs. 0.01% Ti0 2 on Photocatalytic 
Destruction of Benzene at 60 Minutes, Based on ANOM 



1.00 

0.90 

0.80 

0.70 

o 0.60 
O 
~&0.50 

°0.40 

0.30 4 

0.20 

o.io 4 

0.00 



UDL = 0.83 



No Ti0 2 



LDL = 0.68 




urana Ave 
■""rj.75 - * 



0.05% 



■UDLxbar 



Gavg 



■LDLxbar 
-Ti02 Cone 



Figure 4-50. Comparison of Control vs. 0.05% Ti0 2 on Photocatalytic 
Destruction of Benzene at 60 Minutes, Based on ANOM 



127 



1.00 

0.95 

0.90 

(3 0.85 

O 0.80 



075 
0.70 4 
0.65 



.. UDL = 0.93 


UNo Ti0 2 

XI 0.10% 


Grand Ave 
TT.56-" 


LDL = 0.79 



-UDLxbar 



Gavg 



-LDLxbar 
-Ti02 Cone 



Figure 4-51. Comparison of Control vs. 0.10% Ti0 2 on Photocatalytic 
Destruction of Benzene at 60 Minutes, Based on ANOM 



0.70 
0.60 



O 0.50 

8 
O 

0.40 



030 
0.20 



UDL = 0.62 


0.05% 







-/— 


Grand Av( 
■0■.■5~4- , 


LDL = 0.47 


0.01% 





•UDLxbar 



Gavg 



-LDLxbar 
-Ti02 Cone 



Figure 4-52. Comparison of 0.01% vs. 0.05% Ti0 2 on Photocatalytic 
Destruction of Benzene at 60 Minutes, Based on ANOM 



The disinfection results of this study were compared with those 
reported by Patel (1993), Block et al. (1997) and Wei et al. (1994). The latter 
two studies both reported that a concentration of 0.01% Ti0 2 was optimum 
for destruction of Serratia marcescens and Escherichia coli. Patel found 
that consistent inactivation of Serratia marcescens and Pseudomonas 
aeruginosa, both in sunlight and UV light, was achieved with a Ti0 2 
concentration of 0.01%. 



128 

The superior effectiveness of 0.01% and 0.05% Ti0 2 over 0.10% Ti0 2 
concentrations for detoxification of BTEX was not anticipated, as others 
have found 0. 10% Ti0 2 to be the optimum concentration for the destruction 
of BTEX (Goswami et ai. 1993; Oberg 1993). It is conceivable that the 
presence of bacteria had some influence on light penetration, such that 
light penetration at the higher levels of Ti0 2 was not as strong. 
Experiments would need to be designed to consider the effect of the turbidity 
of the water in order to prove this. 
Multiple Parameter Effects 

Evaluation of the effects of multiple parameters helped to clarify the 
role played by each (Ti0 2 , UV light and pH) on the destruction of the tested 
components. When all parameters were considered together, it appeared 
that the most effective treatment for both disinfection (Table 4-21) and 
detoxification (Table 4-22) consisted of photocatalysis with 0.01% Ti0 2 at a 
pH of 4. Figures 4-53 and 4-54 show the effects of light and pH together on 
fractional survival of bacteria and the destruction of benzene. As was 
shown by the ANOM, however, the impact of the pH was not significant, 
and the 0.01% and 0.05% Ti0 2 concentrations do not produce significantly 
different effects. 



Table 4-21. Mean Values for Fractional Survival as a Function of Light, pH 
and Ti0 2 Concentration at t=240 Minutes 

fi0 2 Concentration Light pH 4 Light pH 7 DarkpH4 DarkpHf 

0.00% 0.63 089 i'.2l"" L01 

0.01% 0.00 0.08 0.87 0.96 

0.05% 0.02 0.10 0.75 1.19 

0.10% 0.16 0.05 0.89 1.10 



129 



Table 4-22. Mean Normalized Benzene Concentration After 30 Minutes in 
Ti0 2 Experiments 



TiO> Concentration 


Light pH 4 


Light pH 7 


Dark pH 4 


Dark pi 


0.00% 


1.01 


0.98 


0.90 


1.07 


0.01% 


0.08 


0.02 


0.85 


1.01 


0.05% 


0.31 


0.47 


0.80 


1.05 


0.10% 0.74 


0.79 

.■.v.-.-..-.-.--.-.-.-.-.-.-.-.-.-.-.-.-.\-.-.-.-.-.-.-.-.v.-.-.-.-. 


0.86 1.04 

\v;v;"/; , ; , ; , ;v.v.-.v.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-. ■.-.■.■.■.■.■.-,-.-.■.■.■.- 



Effect of Initial Colony Density on Disinfection 

The large range (1177 x 10 :i cfu/L) and average standard deviation 
(67%) of the initial bacterial colony density (Table 4-23) required the 
exploration of its impact on disinfection. No linear or logarithmic 
relationship was found for initial bacterial colony density with fractional 
survival. A linear regression analysis of initial colony density with N l20 /N 
yielded an r 2 of 0.02, at a 95% confidence level and a p-value of 0.36. For 
ln(N 120 /N ) as a function of initial colony density, least squares linear 
regression at a 95% confidence level yielded an r 2 of 0.01, with a p-value of 
0.22. 

No trend was discernible by graphical examination of the data either. 
Figure 4-55 shows the relationship between initial colony density and 
N 30 /N , using data from individual reactors. The finding of no correlation 
of fractional survival rates with initial colony density was in accord with 
results reported by Li et al. (1996), who compared the destruction of E. coli 
for two different initial coliform densities, 400/L and 110/L, and found only a 
slightly higher destruction rate with the lower initial density, and no 
difference after one hour. 



130 



1.80 
1.60 
1.40 
1.20 
z 100 
z 0.80 
0.60 
0.40 
0.20 
0.00 



1 22 
119 1.08 L 



0.89 



0.20 



0.28 

-,-0.18 



0.10 




uv 

Light 
(4) 



UV 

Light 
(7) 



Dark 
(4) 



Dark 
(7) 



Qt=2 hrs 
Bt=4 hrs 



Figure 4-53. Fractional Survival of Bacteria as a Function of UV Light (29 
W/m 2 ) and pH in Ti0 2 Experiments; Bars are One Standard 
Deviation 



1.40 



1.20 
1.00 - 
^ 0.80 



0.94 1-04V 05 
0.89 




130 minutes 
i60 minutes 



Dark 
pH7 



Figure 4-54. Effect of UV Light (29 W/m 2 ) and pH on the Destruction of 

Benzene in Ti0 2 Experiments; Bars are One Standard Deviation 



Table 4-23. Descriptive Statistics for Initial Colony Density in Ti0 2 
Experiments 



Parameter 


Initial Bacteria Density, cfu JL x 10 4 


Mean 


335 


StdDev 


226 


Min 


67 


Max 

.^^•.^^.V>.v>>>;v.■.^■.■.■.■.•.-.-.•.-.•.•.■.-.■.^■.^-.■.-.-.-.•.•.• 


1244 

.^v.v.-.v.-.^-.v.w.-.-.vAsv.-.-.v.-.-:-.v.-.%\^^^ 



131 



Other Effects 

There were two other effects which merited mention, although the 
experiments were not designed to account for them specifically. Both the 
presence of multiple bacteria species and the combination of bacteria and 
VOCs were likely to have had some impact on both disinfection and 
detoxification. 



9 nn 








1.80 


, * 






1.60 
1.40 


.♦• 






. 1.20 - 

1 1.00 

2 0.80 
0.60 
0.40 - 


•*b * * ♦ 






0.20 
0.00 


***U / • 






•^^^«» • 




500 1 000 


1500 


Initial Colony Density, cfu x 10 3 /L 





Figure 4-55. Initial Colony Count vs. Fractional Survival of Bacteria at t=120 
Minutes for Ti0 2 Photocatalysis 



Interaction between the bacteria and the VOCs was very likely as the 
BTEX could serve as a substrate for the bacteria, causing the organisms to 
multiply. Specifically, P. aeruginosa has been used successfully to degrade 
pentachlorophenol (Premalatha and Suseela Rajakumar 1994). 

Previous photocatalytic disinfection work (Block et al. 1997; Ireland 
et al. 1993; Patel 1993; Wei et al. 1994) examined the destruction of 
individual bacteria species. The longer reaction times experienced in this 
study could be a function of the presence of multiple bacteria species. 



132 

However, as the experiments were not designed to discern this, additional 
work would need to be done in order to confirm this. 
Photocatalvsis vs. Air Stripp in g 

The chemical contaminants (BTEX) are very volatile and therefore 
subject to air stripping (The system tested in these experiments, Ti02 
photocatalysis, yielded positive results at all conditions tested. 
Consequently, the process shows promise for application in small 
communities. However, as evidenced by the efficacy of the 

photosensitization process for the destruction of bromacil, coupled with its 
ineffectiveness for the destruction of benzene and toluene, it is critical that 
any system be tested for the specific contaminants of a water source. 

Table 4-24). In order to determine how much, if any, of the BTEX 
reduction was due to air stripping, dark control experiments were 
conducted. As shown in Figures 4-56 and 4-57, there was essentially no 
reduction observed in any of the BTEX components during the dark 
experiments with Ti0 2 at either pH value. The apparent decrease at 15 
minutes for pH 4 (Figure 4-57) was within the standard deviation of 16% 
and evidence of error encountered in sampling and analysis. The 
precautions taken to limit air stripping, minimal headspace and parafilm 
sealing of the reactor, were sufficient to alleviate transfer of the chemical 
contaminants to the atmosphere. The results reported herein were 
consistent with results reported from outdoor pilot scale experiments 
conducted by (Oberg 1993) and Madabhushi (1997). Both reported less than 
10% reduction in dark tests. Oberg did report on one dark test which 
resulted in an 80-85% reduction of all BTEX components, however, the test 



133 

was conducted with a large air space above the water, wherein a 380 liter 
tank was filled with only 57 liters of water. 

The system tested in these experiments, Ti0 2 photocatalysis, yielded 
positive results at all conditions tested. Consequently, the process shows 
promise for application in small communities. However, as evidenced by 
the efficacy of the photosensitization process for the destruction of bromacil, 
coupled with its ineffectiveness for the destruction of benzene and toluene, it 
is critical that any system be tested for the specific contaminants of a water 
source. 

Table 4-24. Vapor Pressure Values for BTEX components. 



Component 


Vapor Pressure © 25 °C (mm Hg) 


Boiling Point @ 1 atm 


Benzene 


94 








80.1 


Toluene 


28.9 








110.8 


o-Xylene 


6.4 








144 


m-Xylene 


8 








139.3 


p -Xylene 


8.6 


HWOOWWOWOWWWMtOW 


_„„,., 


,,,:,,,,,, 


138.5 

:-:-:->>x-::::-:-;-;;<;:-x-:v:::::-:->:;:<::;::-:-k->>>:-:-:-:<-:v:-^ 







20 40 

Time (minules) 



Benzene 
Toluene 
m&p-Xylene 
-o-Xylene 



Figure 4-56. Normalized Concentrations of BTEX Components in pH 7 Dark 
Experiments with 0.01% Ti0 2 



134 




20 40 

Time (minutes) 



Benzene 
Toluene 
mAp-Xylene 
o-Xylene 



Figure 4-57. Normalized Concentrations of BTEX Components in pH 4 Dark 
Experiments with 0.01% Ti0 2 



Summary 

Examination of the conditions under which Ti0 2 photocatalysis was 
most effective brings up two aspects for consideration. On the positive side, 
pH was not a significant factor and no pH adjustments would be required. 
The specificity of the concentration of Ti0 2 , however, is a disadvantage for 
the applications considered here. The dosage of Ti0 2 must be fairly tightly 
controlled as too much could result in inhibition of the photocatalytic 
reaction. However, the low Ti0 2 dosage requirements do offer an advantage 
in that operational costs are minimized. 

In order for this process to be determined feasible for application, 
two areas of research should be addressed. First, the issue of 
immobilization or separation of the catalyst and associated cost, must be 
examined. This may be accomplished via the use of a small filter, however, 
such a system should be tested. Secondly, the system must be tested over a 
much broader range of microbiological and chemical contaminants, 



135 

including viruses. Site specific testing is a must, as microbiological species 
may differ from one locale to the other. 

TiO „ Photocatalvsis Combined With Methylene Blue 

Several experiments were conducted using both Ti0 2 and MB. These 
combination experiments were conducted in order to determine if the use of 
a dye in combination with Ti0 2 would enhance the photochemical process 
by extending the range of photons available for photochemical reaction. 

In order to ensure reproducibility of the results, each set of 
experiments was conducted three times. Four reactors were run at a time, 
each reactor containing either no photochemical, 0.01% Ti0 2 , 5 mg/L MB, 
or a combination of 0.01% Ti0 2 and 5 mg/L MB. A complete set of 
experiments was defined as two groups of four reactors, one group in 
sunlight and one group in the dark. 

Samples were taken from each reactor at time intervals of 0, 5, 15, 30, 
60, 120 minutes and refrigerated immediately. Three replicates from each 
sample were plated for microbiological analysis. The remainder of the 0, 30 
and 120 minute samples was refrigerated and saved for chemical analysis. 

For the experiments conducted in sunlight, both the total insolation 
and the UV light intensity were measured and recorded over the duration 
of the experiment. Total insolation ranged from 433 W/m 2 to 853 W/m 2 , and 
the total UV intensity measurements ranged from 25 to 40 W/m 2 . The 
recorder was jammed for approximately the last half hour of the set three 
experiment. Values for that portion of the experiment were estimated 
based on measurements before the recorder jammed and the maximum 



136 

and minimum values during this time period (as determined by the high 
and low of the pen marks). The average total insolation measured in each 
experiment is given in Table 4-25, and graphs of the total insolation are 
shown in Appendix B. 

Table 4-25. Measured Sunlight Intensity in Combination Experiments 

Set ^ Total Avg Insolation, W/n?" Total ''Avg 'UV,' Win 1 

#2 853 40 

#3 433 25 



General Comments About Experimental Data 

The average standard deviation of the disinfection data was 13%. 
Plates on which the colonies were not individually identifiable and those 
with severe contamination were not counted, which resulted in the loss of 
11-37% of the 144 plates in a given experimental set. 

The average standard deviations of the detoxification data were much 
higher than in either of the other experimental groups, 23% for benzene 
and 56% for toluene. However, when normalized concentrations were 
used, the average standard deviation was lower, 14% for benzene and 17% 
for toluene, although they still exceeded the values of the other two 
experimental groups. The average standard deviation values are given in 
Table 4-26. 

Sample loss for detoxification occurred when the sample was 
dropped and broken prior to analysis, which occurred once in experimental 
set number one. The dropped sample was an initial sample, 43 , and the 5 



137 

minute sample was substituted. Chemical samples were generally 
analyzed within two weeks of the experiment. 

Table 4-26. Average Standard Deviations for all Combination Experiments 



Benzene (ppb) 

-:-X-X%-:%<%%<oC-X-x-:-:-:-:-:-:o:o*:->x<^ 

StdDev Avg 


Toluene (ppb) 

" StdDev Avg' 


E.Coli (cfuxltfVL 
StdDev Avg 


Raw Data 120 511 
Normalized Data 0.11 0.77 


199 357 
0.12 0.72 


119 651 
0.13 0.50 



Statistical Treatment of the Data 

The data were treated as outlined in the section on dye 
photosensitization. No specific adjustments were required for the data, 
with the exception of normalizing negative percentages of destruction to 
zero. No outliers were observed. 
Disinfection 

Since both MB and Ti0 2 increased the efficiency of disinfection of E. 
coli bacteria over sunlight or UV light alone, it was anticipated that the 
combination would be better than either alone. However, as shown in 
Figure 4-58, there was little difference between using Ti0 2 alone, MB alone 
or a combination of Ti0 2 and MB. The use of a photochemical, however, did 
improve disinfection over sunlight alone (Table 4-27). In the presence of 
MB, either with or without Ti0 2 there was a 95% coliform reduction within 
5 minutes and complete disinfection within 15 minutes. A coliform 
reduction of 95% was reached by 15 minutes with Ti0 2 and not until GO 
minutes in sunlight alone. Total disinfection was not observed until the 30 
minute samples with Ti0 2 and 120 minutes in sunlight alone. 



138 



The data were analyzed by ANOM (as outlined previously) to 
determine the effect of sunlight and photochemicals on disinfection. The 
fractional survival at 5, 15 and 30 minutes were analyzed in this manner. 
The grand average values for E. coli destruction at 5, 15 and 30 minutes 
were 0.63 (±0.16), 0.57 (±0.14), 0.52 (±0.12), respectively. The general values 
for the ANOM are shown in Table 4-27. 

For determination of the effect of sunlight, the sample sets were 
divided into two subgroups (k=2) with twelve observations per subgroup 

(n=12). The corresponding table values were v = 17.8, d,* = 3.304, and, for a = 

0.05, H = 1.49. These values, along with the values in Table 4-28, were used 
to determine the decision limits using Equations 4-4 to 4-6. The calculated 
subgroup averages, shown in Table 4-29, were then plotted on a chart with 
the decision limits, and the significance of the presence of sunlight was 
determined. As anticipated, the presence or absence of sunlight was a 
statistically significant factor in all of the sample sets, as shown in Figure 
4-59. 




Avg S.D. = 16.9% 





Control 


— Q- 


-Ti02 


—br 


MB 


-X- Both 



50 100 

Time (minutes) 



150 



Figure 4-58. Destruction of E. coli in Sunlight 0,- A „ = 433-853 W/m 2 , 1,^ Avg 
= 25-40 W/m 2 ) in Combination Experiments 



139 



Table 4-27. Mean Fractional Survival (±14.1%) of E. Coli in Combination 
Experiments 

Control Samples 61% TiOg 

Sunlight Dark Sunlight Dark 

' N5/N0' 1.10 1.21 0.62 0.61 

N 15 /N 0.99 1.32 0.05 0.91 

N 30 /N 0.63 1.30 0.00 0.82 

N^/No 0.05 1.29 0.00 0.55 

tWN 8 0.00 1.11 0.00 0.94 

5mg/LMB 0.1% TiQ 3 & 5 mg/L MB 

Sunlight Dark Sunlight Dark 

N 5 /N 0.04 0.70 0.01 0/73 

N 1S /N 0.00 0.66 0.00 0.64 

N 30 /N 0.00 0.64 0.00 0.77 

Ngo/No 0.00 0.36 0.00 0.61 

N 120 /N„ 0.00 0.65 0.00 0.59 



Table 4-28. Calculated ANOM Values for Combination Experiments 



Sample Set 



Grand Average, X 



Avg Std 
Dev 



Avg Range 



Estimated 
SD(X) 



E. coli @ t=5 minutes 
E. coli @ t= 15 minutes 
E. coli @ t=30 minutes 
Benzene @ t= 30 minutes 
Benzene @ t= 120 minutes 
Toluene @ t= 30 minutes 
Toluene @ 120 minutes 



0.63 
0.57 
0.52 
0.69 
0.84 
0.81 
0.63 



0.16 


0.36 


0.14 


0.31 


0.12 


0.30 


0.01 


0.22 


0.12 


0.28 


0.14 


0.33 


0.01 


0.23 



0.21 
0.18 
0.16 
0.11 
0.15 
0.16 
0.12 

.v.v.-.w:*:v:-.-;-:^-:-.-:-:-.-:-.vv; 



Table 4-29. Sunlight Subgroup Averages for Combined Experiments. 
Values are Fractional Survival of Bacteria and Normalized Chemical 
Concentration 





Sunlight ( 433-853 W/m 2 ) 




Dark 






X 


S 


R 


X 


S 


R 


E. coli @ t= 5 minutes 


0.44 


0.05 


0.12 


0.81 


0.26 


0.60 


E. coli @ t=15 minutes 


0.26 


0.02 


0.05 


0.88 


0.25 


0.56 


E. coli @ t= 30 minutes 


0.16 


0.06 


0.15 


0.88 


0.19 


0.45 


Benzene @ t= 30 minutes 


0.76 


0.14 


0.32 


0.93 


0.10 


0.24 


Benzene @ t= 120 minutes 


0.55 


0.08 


0.18 


0.83 


0.11 


0.26 


Toluene @ t= 30 minutes 


0.68 


0.17 


0.39 


0.93 


0.11 


0.26 


Toluene @ t= 120 minutes 


0.48 


0.05 











140 

In order to clarify the impact of the photochemicals on disinfection, 
ANOM was performed. The data were divided into four subgroups based on 
the photochemical used in the reactor. This gave an n value of 6 samples 
per subgroup and a k value of 4 subgroups for each sample set. The 

corresponding table values were v = 18.1, d 2 * = 2.569, and, for a = 0.05, H = 

2.35. These values, along with the values in Table 4-28, were used to 
determine the decision limits using Equations 4-4 to 4-6. 

The calculated subgroup averages (Table 4-30) were plotted on a chart 
with the decision limits, and the significance of photochemicals was 
determined. The presence or absence of photochemical was a statistically 
significant factor in all of the sample sets, as shown in Figure 4-60. 



Table 4-30. Photochemical Subgroup Averages for Combination Experiments; 
Values are Fractional Survival of E. coli and Normalized Chemical Concentration 

■x<o>x-x->:-x%->>:<<<<<<'>>>x-:-:o:-x->x-:->>>>>:-:-:-:-'-'.:.r-:.x.::--- 



Control 0.01% TiO, 5 mg/L MB Both 

xsRxsRx s Rx s R 

Rcoii @t=5min 1.07 0.06 0.11 0!57 0.30 0.59 6.32 0.20 0.40 6.40 0.02 ftoT 

E.coli @t=15min 1.08 0.03 0.05 0.55 0.07 0.14 0.30 0.20 0.38 0.28 0.16 0.32 

E.coli @t=30min 0.81 0.11 0.22 0.42 0.10 0.20 0.30 0.12 0.24 0.38 0.10 0.19 

Benzene @ t=30 min 0.89 0.08 0.16 0.83 0.21 0.42 0.97 0.06 0.11 0.75 0.14 0.29 

Benzene @t=120min 0.81 0.14 0.28 0.50 0.08 0.15 0.86 0.09 0.18 0.65 0.12 0.24 

Toluene @t=30 min 0.85 0.11 0.22 0.77 0.18 0.35 0.92 0.04 0.08 0.69 0.20 0.39 

Toluene @ t=120 min 0.77 0.12 0.25 0.44 0.05 0.10 0.74 0.16 0.32 0.55 0.10 0.20 



In order to discern if there was any differentiation in the treatments, 
the different photochemical subgroup averages were plotted against each 
other. The new decision limits were based on a k of 2 and an n of 6, which 
changed the table values to v = 9.2, d 2 * = 2.603, and, for a = 0.05, H = 1.6. The 
plotted subgroup averages are shown in Figures 4-61 to 4-63. 



141 



(a) 



90 


0.80 - 


-UDL = 0.72 




XDark 




0.70 

0.60 

Z> 0.50 - 

z 0.40 - 






/ Grand Avg 


I 


LDL = 0.54 


XSun 


ight 


0.30 - 










0.20 










0.10 - 










00 




















i mi v 


-LDLx -■ 



















(b) 



0.90 
0.80 
0.70 
0.60 

Z 0.50 

1 

z 0.40 

0.30 
0.20 

0.10 
0.00 







5 Dark 


UDL = 0.65 









J- 


Grand Avg 

D"57 


LDL = 0.49 








XSunlight 

















-UDLx 



-LDLx Gavg 



■Light 



(O 



0.90 
0.80 
0.70 
0.60 
Z 0.50 
1 0.40 
0.30 
0.20 
0.10 
0.00 



._ 




rDafx 


UDL = 0.59 






.= 


J. 


Cjrand Avg 
0"52 ' 


LDL ■ 0.45 






- 


XSunlight 





-UDLx 



-LDLx Gavg — K — Light 



Figure 4-59. Significance of Sunlight (L^ AvK = 433-853 W/m 2 , l m Ave = 25-40 



UV, Avg 



W/m ) on E. coli Destruction, Based on ANOM, in Combination 
Experiments; (a) 5 Minutes (b) 15 Minutes (c) 30 Minutes 



142 

The ANOM demonstrated clearly what the graphical display of the 
data suggested. There was no statistically significant difference between 
the use of MB, Ti0 2 or a combination of the two in photochemical 
disinfection. 
Detoxification 

The addition of MB to the Ti0 2 photocatalyzed reaction appeared to 
have an inhibitory effect on detoxification. After 120 minutes in sunlight 
(I T ot, Av g = 433-833 W/m 2 , I UVi Avg = 25-40 W/m 2 ), reactors dosed with 0.01% Ti0 2 
showed a 94% reduction of benzene and a reduction of toluene below 
detectable limits (Figure 4-64). However, when 0.01% Ti0 2 was combined 
with 5 mg/L MB and exposed to the same intensity sunlight for 120 
minutes, only a 65% and 70% reduction in benzene and toluene, 
respectively, was observed. The mean concentrations of both benzene and 
toluene in the combination experiments are shown in Table 4-31. 

While the conclusions seemed to be clear, an ANOM was performed 
to clarify the distinction between the use of Ti0 2 alone and the combination 
of Ti0 2 and MB. The data were divided into four subgroups as outlined 
above in the disinfection section, with the same values used for calculation 
of decision limits, for both four subgroups and two subgroups. The 
subgroup averages are shown in Table 4-30. Selected ANOM charts are 
shown as Figures 4-65 to 4-68. 



143 



(a) 



1.20 




0.00 



— UDLxbar 
■-Gavg 



Grand_Aya 
~ 0.63 



-LDLxbar 
-Photochemical 



(b) 



1.20 
1.00 
0.80 

o 

"2 0.60 

2 

0.40 
0.20 
0.00 



-UDL = 0.74 


Q Control 








Grand Avg_ 




Ti0 2 N. 


0.57 


LDL = 0.40 




-fcW — DBoth 



-UDLxbar 



Gavg 



-LDLxbar 
-Photochemical 



(0 



0.90 
0.80 
0.70 
0.60 
:0.50 
:0.40 
0.30 
0.20 
0.10 
0.00 





D Control 


.UDL = 0.67 


\ 




\ Grand Avg_ 


_. 


\ d u. ° 52 
ViO, ?oth 


LDL = 0.37 


NhjT 











-UDLxbar 



Gavg 



-LDLxbar 
-Photochemical 



Figure 4-60. Significance of Photochemical on E. coli Destruction, Based on 
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15 
Minutes (c) 30 Minutes 



144 



(a) 



u.ou 

0.70 


UDL = 0.63 


0.60 - 
0.50 ■ 


Ti0 2 °Sw 




Grand Avg_ 


0.40 ■ 




\n MB 


049 


0.30 - 

0.20 - 

0.10 ■ 
n nn - 


-LDL = 0.35 



-UDLxbar 



Gavg 



-LDLxbar 
-Photochemical 



(b) 



0.60 
0.50 
0.40 - 

o 

?, 0.30 

2 

0.20 
0.10 - 
00 










UDL = 0.52 




aj[i0 2 


***n mb 


Grand Avg_ 
0.41 


LDL = 0.29 






















Gavg 

























(0 



0.50 

0.45 

0.40 

0.35 
o0.30 
J 0.25 
Z 0.20 

0.15 

0.10 ■- 

0.05 - 

0.00 



UDL = 0.47 













o 


^ip2 




Grand Avq_ 


-- 




^a MB 


0.37 


"LDL ■ 0.26 








- 









-UDLxbar 



Gavg 



-LDLxbar 
■Photochemical 



Figure 4-61. Significance of Ti0 2 vs MB on E. coli Destruction, Based on 
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15 
Minutes (c) 30 Minutes 



145 



(a) 



0.80 

070 4uDL = 0.63 
60 Ti0; 
050 4 \ S 



%0.AO 

z 




0.30 -j LDL = 0.35 

0.20 

0.10 

0.00 



Both 



-UDLxbar 



Gavg 



Grand Avg 



-LDLxbar 
-Photochemical 



(b) 



60 


0.50 - 


UDL = 0.52 




n,Ti02 




0.40 ■ 




Grand Av< 


L 






0.40 


^0.30 - 

z 

0.20 ■ 




Tl Both 




LDL = 0.28 




0.10 - 








00 - 






























Gavg 


— O— - Photochemical 

















(0 



0.60 

0.50 
0.40 
>,0.30 
0.20 
0.10 
0.00 



UDL = 0.50 




T1O2 




Grand Avq 


Both 


fj4D 


LDL = 0.30 



-UDLxbar 



Gavg 



-LDLxbar 
-Photochemical 



Figure 4-62. Significance of Ti0 2 vs Both onE. coli Destruction, Based on 
ANOM, in Combination Experiment; (a) 5 Minutes (b) 15 
Minutes (c) 30 Minutes 



146 



(a) 



(b) 



(0 



060 
0.50 
0.40 - 

1 0.3, 

z 

0.20 
0.10 

0.00 



UDL = 0.51 


MB 


□ - 


Grand Avq 
0.37 






-' 


Both 




LDL = 0.23 













-UDLxbar 



Gavg 



■LDLxbar 
■Photochemical 



0.60 



0.40 

o 

^0.30 

2 

0.20 
0.10 
0.00 



- UDL = 0.45 


MB 




Grand Avg 




Both 


0"53 


LDL = 0.21 



-UDLxbar 



Gavg 



-LDLxbar 
-Photochemical 



0.60 
0.50 
0.40 

>0.30 

z 

0.20 
0.10 
0.00 



. UDL = 0.43 


MB ""^ 


^-Q Both 


Grand Avg 
7T32 


LDL = 0.22 



■UDLxbar 



Gavg 



-LDLxbar 
■Photochemical 



Figure 4-63. Significance of MB vs Both on E. coli Destruction, Based on 
ANOM, in Combination Experiments; (a) 5 Minutes (b) 15 
Minutes (c) 30 Minutes 



147 



(a) 




- Control 
-TI02 

MB 

Both 



50 100 

Time (minutes) 




000 



50 100 

Time (minutes) 



■ Control 
-Ti02 
-MB 
-Both 



(b) 

Figure 4-64. Normalized Concentration as a Function of Time in Combination 
Experiments I Tot A _ = 433-833 W/m 2 , 1^ Avg = 25-40 W/m 2 ; (a) 



, Avg 

Benzene (b) Toluene 



Table 4-31. Mean Concentration (ppb) of Benzene (±120) and Toluene (±199) 
in Combination Experiments; I Tot Avg = 433-833 W/m 2 , 1^ Avg = 25-40 W/m 2 



Benzene 
Time (min) 

30 
120 



Sunlight Dark 

Control 



.-.-^-.-.-.-.-.-.-.-.-.-.-.•.-.•.•.■.•.•.■.■.■.•.■.•.•.-:*.'.-.-.*:->. 



Sunlight Dark 

0.01% TiO, 



542 
459 
430 



649 
640 
535 



576 

233 

17 



677 
620 

588 





5 mg/L MB 


Both 







490 672 


549 714 




30 


485 644 


372 607 




120 


421 538 


231 581 




Toluene 


Sunlight Dark 


Sunlight Dark 




Time (min) 


Control 


0.01% Ti0 2 







413 445 


439 447 




30 


348 436 


148 428 




120 


320 392 


1 387 






5 mg/L MB 


Both 







371 462 


451 456 




30 


352 448 


254 437 




120 


293 315 


128 393 





148 



(a) 



1 00 


UDL = 0.99 














□ MB 




0.90 




l-Qontrol / 




Grand Avg 


0.80 




Ti0 2 




0.84 


O 

o 

~$0.70 
O 








bBoth 










LDL = 0.70 








0.60 










0.50 
n An . 











-UDLxbar 



Gavg 



■LDLxbar 
■Photochemical 



(b) 




■UDLxbar 



Gavg 



Grand Avg 
-- (TS9" - - 



Both 



■LDLxbar 
■Photochemical 



Figure 4-65. Significance of Photochemical on Benzene Destruction, Based 
on ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 



149 



(a) 



1-0 UDL = 0.96 



0.90 
0.80 

O 

1*0.70 
O 

0.60 
0.50 
0.40 




LDL = 0.65 



■UDLxbar 



Gavg 



Grand_Aya 



Both 



■LDLxbar 
■Photochemical 



(b) 



0.80 

0.75 

0.70 

0.65 

o 0.60 
O 
^0.55 

"0.50 

0.45 

0.40 

0.35 

0.30 



-- UDL = 0.74 


q Control MB 




-- 


A f\ 


Grand Avg 


- 


V 


0~53 
□ Both 


LDL = 0.51 


OTi0 2 





-UDLxbar 
■Gavg 



LDLxbar 

-O — Photochemical 



Figure 4-66. Significance of Photochemical on Toluene Destruction, Based 
on ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 



150 



(a) 



1.00 

0.95 

0.90 

0.85 

o 0.80 
O 

-&0.75 
O 
0.70 

0.65 

0.60 

0.55 

0.50 



UDL = 0.84 


-- 




Both 


Grand Ayg_ 
0.75 


-- 


Ti0 2 


j.LDL = 0.65 









-UDLxbar 



Gavg 



-LDLxbar 
■Photochemical 



(b) 





UDL = 0.61 




Both 




0.60 


/ Grand Avg 


0.50 




/ 




0.55 


J 0.40 - 


LDL = 0.48 


u 

Ti0 2 






~S 










O 0.30 - 










0.20 ■ 










0.10 - 
n nn 











-UDLxbar 



Gavg 



■LDLxbar 
-Photochemical 



Figure 4-67. Significance of Ti0 2 vs Both on Benzene Destruction, Based on 
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 



151 



(a) 



(b) 



1 .uu 
0.90 


UDL = 0.80 








80 










0.70 






^Both 


Grand Avg 
0"B9 


0.60 




TioT 3- ' 


% 050 
0.40 


LDL = 0.59 
















0.30 t 








0.20 • 








0.10 
n nn 











-UDLxbar 



Gavg 



-LDLxbar 
-Photochemical 













0.70 
0.60 

00.50 

o 
0.40 

0.30 - 

20 


UDL = 0.56 










/'Both 


Grand Av< 


L 


™~7 




fJ.38 - ' 


LDL = 0.40 






















-LDLxbar 

—Photochemical 




Gavg 



















Figure 4-68. Significance of Ti0 2 vs Both on Toluene Destruction, Based on 
ANOM, in Combination Experiments; (a) 30 Minutes (b) 120 
Minutes 



Examination of the ANOM charts showed that differences between 
control and Ti0 2 were not apparent until 120 minutes (Figures 4-65 and 4- 
66). By 120 minutes, there was a statistically significant difference between 
the reactors which contained Ti0 2 only and both the control reactors and 
the reactors containing only MB. The inhibitory effect of MB in the 
combination reactor was evident for benzene by 120 minutes (Figure 4-67), 
though not for toluene (Figure 4-68). 



152 

Summary 

The use of dye in conjunction with Ti0 2 did not enhance the 
photochemical process for either disinfection or detoxification. While it had 
no apparent effect in the disinfection reactions, the dye acted as an 
inhibitory agent in the detoxification process. The reduction of efficacy with 
the addition of MB was possibly due to scavenging of hydroxyl radicals by 
the MB. While this has not been reported for MB, scavenging has been 
reported for other oxidizing agents, such as hydrogen peroxide (Blake 1994). 

Kinetic Considerations 

For a quantitative comparison of experimental conditions, 
experimental reaction rate constants, k, were calculated using the first 
order reaction rate equation shown below. Rate constants are presented 
only for those experiments in which destruction of contaminants occurred. 

ln(CyC) = kt ( 4-7 ) 

where: 

C = Initial concentration (or colony density) 

C = Concentration (or colony density) at time, t 

t = time, in minutes 

k = calculated rate constant (min 1 ) 
Detoxification 

Experimental first order rate constants are presented for the 
destruction of benzene, toluene and xylene isomers by Ti0 2 photocatalysis in 
UV light, Ti0 2 photocatalysis in sunlight and the use of Ti0 2 photocatalysis 
combined with MB. The calculated rate constants are shown in Table 4-32. 



153 

The higher rate constants correspond to faster reaction time. For Ti0 2 
photocatalysis the fastest reaction rate (k = 0.12 min' 1 ) was observed in 
reactors illuminated by UV lamps (29 W/m 2 ) which contained 0.01% Ti0 2 
and water adjusted to pH 7. 



Table 4-32. Experimental First - Order Rate Constants (min 1 ) for Ti0 2 
Photocatalytic Experiments 



UV Light (29 W/m' 2 ) @ pH 4 










0.01% Ti0 2 
0.05% Ti0 2 
0.10% Ti0 2 


Benzene 
0.08 
0.03 
0.009 


Toluene 
0.11 
0.03 
0.009 


m&p-Xylene 
0.09 
0.03 
0.01 


o-Xylene 

0.08 
0.03 
0.02 


UV Light (29 W/m 2 ) @ pH 7 


0.01% Ti0 2 
0.05% Ti0 2 
0.10% Ti0 2 
Sunlight du^^s 433-853 W/m 


Benzene 
0.12 
0.02 
0.006 


Toluene 

0.12 
0.02 
0.007 

25-4Tw/m 2 )rpH 


m&p-Xylene 

0.12 

0.02 

0.007 

was not measured 


o-Xylene 
0.10 
0.02 
0.01 


0.01% Ti0 2 
0.01% Ti0 2 & 5 mg/L MB 


0.02 
0.007 


0.04 
0.01 


N.A. 
N. A. 


N.A. 
N.A. 



The calculated first-order reaction rate constants were consistent 
with the previous analysis of the data, wherein 0.01% Ti0 2 was found to be 
most effective, though not significantly different from 0.05% Ti0 2 . The rate 
constants obtained in these experiments were consistent with those 
reported by Madabhushi (1997) for indoor tests at a slightly higher UV 
intensity (35 W/m 2 ) and 0.1% Ti0 2 . He reported values ranging from 0.1 - 
0.15 for p-Xylene and values of 0.13 - 0.14 for all other components. The 
values for his outdoor tests also compared favorably to the value obtained in 
this experiment. He reported a consistent value of k=0.03 min' 1 with 1^ av = 
31-35 W/m 2 and 0.1% Ti0 2 ,compared to 0.02 min 1 in sunlight (I m avg = 25^0 
W/m 2 ) with 0.01% Ti0 2 in this study. 



154 

Disinfection 

While reaction rate constants as a function of time have not been 
reported for photochemical disinfection, some of the reported results have 
appeared to follow first order kinetics with time (Block et al. 1997). Most of 
the data fit well to first-order reaction rate kinetics as shown in Table 4-33. 
Several graphical examples are given in Figures 4-69 to 4-72. These results 
can be used as a basis for comparison of the processes studied in this 
research. 






Table 4-33. Correlation Statistics for Least Squares Linear Regression of 
Kinetic Data; Confidence Level is 95% 

UV Light (29 W/m 2 ) @ pH 4 UV Light (29 W/m 2 ) @ pH 7 

r 2 p-value r 2 p-vaiue 

0.01% fi02 6.84 0.0077 0.97 0.0007 

0.05% Ti02 0.90 0.0025 0.96 0.0002 

0.10% Ti02 0.44 0.0257 0.55 0.0188 

^^^^^^^^^^^9^^2 ""Sta [jrijgg T(e6T 89TV wSjffitT 'j^g^f" 

Omg/LMB 0.79 0.0266 0.95 0.0003 

0.1 mg/L MB 0.30 0.0415 0.76 0.0009 

lmg/LMB N.A. N.A. 0.14 0.0091 

5 mg/L MB 0.49 0.0899 N.A. N.A. 

10 mg/L MB N.A. N.A. N.A. N.A. 

Omg/LRB 0.99 0.0001 0.99 0.0001 

0.1 mg/L RB 0.92 0.001 0.81 0.0010 

1 mg/L RB 0.95 0.0003 0.95 0.0003 

5 mg/L RB 0.91 0.0012 0.91 0.0012 

10 mg/L RB 0.88 0.0022 0.88 0.0022 



155 



A 








3.5 


/♦ 








3 










z 25 
I 2 

S 1.5 

1 


♦ / 










+ Observed 




Predicted 






0.5 ■ 










n ^ 










c 


) 50 100 


150 






Time (minutes) 







Figure 4-69. Least Squares Linear Regression of First Order Rate Equation 
for Disinfection in UV Light (29 W/m 2 ) with 0.05% Ti0 2 and pH 
= 4; r 2 = 0.90, p-value = 0.0025 




♦ Observed 
Predicted 



50 100 

Time (minutes) 



150 



Figure 4-70. Least Squares Linear Regression of First Order Rate Equation 
for Disinfection in UV Light (29 W/m 2 ) with 0.10% Ti0 2 and pH 
= 7; r 2 = 0.55, p-value = 0.019 



156 




1 fin 






1.40 - 










1.20 - 










- 1.00 - 

z 

z 0.80 

- 0.60 - 












» Observed 
Predicted 








0.40 - 










0.20 

n nn < 










U.UU ^ | 

10 20 30 






Time (minutes) 




Figure 4-71. Least Squares Linear Regression of First Order Rate Equation 
for Disinfection in Sunlight (715-775 W/m 2 ) with no 
photochemical and pH = 10; r 2 = 0.99, p-value = 0.0001 




6 00 








5.00 


( 


► 




_4.00 - 

z 

^ 3 00 

2.00 - 


/S ♦ 










+ Observed 
Predicted 








1.00 - 
n nn < 


fc< i i 








U.UU % I 

20 40 60 






Time (minutes) 




Figure 4-72. ] 
fo 
Pi 


..east Squares Linear Regression of First Order R 
r Disinfection in Sunlight (746-856 W/m 2 ) with 1 1 
i = 7; r 2 = 0.95, p-value = 0.0003 


ate Equation 
ng/L RB and 


Table 4-34 is a comparison of the experimental first order rate 


constants, k, for all of the disinfection experiment sets. Where no values 


were reported, the reactions occurred too quickly to accurately calculate a 


rate constant. Examination of the experimental rate constants gave a 


hierarchy of processes for disinfection. T 


he 


largest rate constant, 



157 

corresponding to the fastest reaction time, 0.45 min' 1 , was in the reactors 
containing 5 mg/L MB at pH 10, with 0.1 mg/L MB coming in a close second 
at 0.24 min 1 . It is important to note that values could not be calculated for 
the other concentrations of MB because the reactions occurred too quickly to 
collect enough data for determination of rate constants. The calculated rate 
constants for all other conditions were similar in value, ranging from 0.09 - 
0.01 min 1 . 



Table 4-34. First Order Rate Constants for All Photochemical Disinfection 
Experiments 

UV Light (29 W/m') 9 pH 4 "UV Light (29 W/m a ) # pH 7 
0.01% Ti02 0.05 0.03 

0.05% Ti02 0.03 0.03 

0.10% Ti02 0.01 0.03 

6 mg/L MB 0.09 0.07 

0.1 mg/L MB 0.24 0.05 

1 mg/L MB N.A. 0.07 

5 mg/L MB 0.45 N.A. 

10 mg/L MB N.A. N.A. 

Sunlight '"(715-77S ^^^^^^^W^^^^^^^^^W^W^^^ 

6m 



mg/L RB 


0.05 


0.1 mg/L RB 


0.09 


1 mg/L RB 


0.09 


5 mg/L RB 


0.08 


10 mg/L RB 


0.08 



0.06 
0.09 
0.08 
0.08 



General Summary of Results 

The only process which was effective for destruction of all of the 
contaminants was Ti0 2 photocatalysis. A quantitative comparison of the 
experimental sets performed in this study is shown in Table 4-35. 



158 



Table 4-35. Time to Complete Destruction by Photochemical Treatment. 



Photochemical 



Light 



pH 



Benzene 
Destruction 



Bacteria 
Destruction 



0.1 mg/L MB 
1 mg/L MB 
5 mg/L MB 
10 mg/L MB 
0.1 mg/L MB 
1 mg/L MB 
5 mg/L MB 
10 mg/L MB 
0.1 mg/L MB 
1 mg/L RB 
5 mg/L RB 
10 mg/L RB 
0.1 mg/L RB 
1 mg/L RB 
5 mg/L RB 
10 mg/L RB 
0.01% Ti0 2 
0.05% Ti0 2 
0.10%TiO 2 
0.01% Ti0 2 
0.05% Ti0 2 
0.10%TiO 2 
0.01% Ti0 2 
TiO ? &MB 
Notes: values in 
measured. 



Sunlight, 665-891 W/m 2 
Sunlight, 665-891 W/m 2 
Sunlight, 665-891 W/m 2 
Sunlight, 665-891 W/m 2 
Sunlight, 542-696 W/m 2 
Sunlight, 542-696 W/m 2 
Sunlight, 542-696 W/m 2 
Sunlight, 542-696 W/m 2 
Sunlight, 746-856 W/m 2 
Sunlight, 746-856 W/m 2 
Sunlight, 746-856 W/m 2 
Sunlight, 746-856 W/m 2 
Sunlight, 715-775 W/m 2 
Sunlight, 715-775 W/m 2 
Sunlight, 715-775 W/m 2 
Sunlight, 715-775 W/m 2 

UV, 29 W/m 2 

UV, 29 W/m 2 

UV, 29 W/m 2 

UV, 29 W/m 2 

UV, 29 W/m 2 

UV, 29 W/m 2 
Sunlight, 433-853 lol , 25-40 OT W/m 2 
Sunlight, 433-853,,!, 25-40^ W/m 2 



7 


(20%, 240 min) 


240 min 


7 


(20%, 240 min) 


240 min 


7 


(35%, 240 min) 


240 min 


7 


(23%, 240 min) 


120 min 


10 


(33%, 240 min) 


60 min 


10 


(29%, 240 min) 


5 min 


10 


(23%, 240 min) 


120 min 


10 


(37%, 240 min) 


5 min 


7 


(23%, 240 min) 


120 min 


7 


(19%, 240 min) 


(99.7%, 240 min 


7 


(27%, 240 min) 


120 min 


7 


(26%, 240 min) 


240 min 


10 


(15%, 240 min) 


240 min 


10 


(35%, 240 min) 


120 min 


10 


(36%, 240 min) 


120 min 


10 


(34%, 240 min) 


120 min 


4 


(99%, 60 min) 


60 min 


4 


(78%, 60 min) 


(97%, 60 min) 


4 


(39%, 60 min) 


(88%, 60 min) 


10 


60 min 


240 min 


10 


(74%, 60 min) 


240 min 


10 


(28%, 60 min) 


(91%, 60 min) 


n m 


(94%, 240 min) 


30 min 


n m 


(56%, 240 min) 


15 min 



() indicate maximum destruction achieved by time indicated; nm = not 



In almost all processes in which destruction was observed the key 
factors were: (1) the absence and presence of light, (2) the absence and 
presence of photochemical, and (3) the concentration of photochemical. The 
one exception was in Rose Bengal disinfection experiments, wherein 
neither light nor photochemical had any effect. The significance of these 
two parameters was indicative of photochemical action. Minimal pH 
effects were observed in disinfection with rose bengal. The lack of effect of 
RB concentration on disinfection in these experiments indicates that no 
photochemical reaction occurred with RB. 



CHAPTER 5 
SUMMARY AND CONCLUSIONS 

Summary 

Laboratory scale studies were conducted to assess the potential for 
solar photochemistry to serve as a feasible technology for drinking water 
treatment. The objectives defined for the research were to (1) assess the 
ability of photochemical processes to effect simultaneous treatment of 
chemical and microbiological pollutants and (2) to compare efficacies of 
photosensitization, photocatalysis and combined photosensitization and 
photocatalysis. 
Process Efficacy Comparison for Simultaneous Treatment 

The three processes investigated were: 1) heterogeneous Ti0 2 
photocatalysis, 2) homogeneous dye photosensitization with methylene blue 
and rose bengal, and 3) a combination of the heterogeneous and 
homogeneous process with Ti0 2 and methylene blue. 

Of the three processes, only one, Ti0 2 photocatalysis, successfully 
demonstrated simultaneous detoxification and disinfection of the 
components tested. The dye sensitization process with methylene blue 
achieved disinfection but did not achieve destruction of the chemical 
contaminants tested. When the three processes were compared directly (in 
the combination experiments), there were no differences in disinfection 



159 



160 

efficacy. However, the Ti0 2 photocatalytic process was significantly more 
effective for detoxification. 
Drinking Water Quality 

Where photochemical action occurred in the systems studied, the 
contaminants either were reduced or demonstrated clear potential for 
reduction below standard water quality parameters. 

The Ti0 2 photocatalytic process was able to meet or exceed the US 
EPA maximum contaminant level for benzene of 5 ppb (Kawamura 1991). 
The requirements for toluene (1 ppm) and combined xylenes (10 ppm) were 
higher than the starting point of this study. Both MB photosensitization 
and Ti0 2 photocatalysis exceeded the requirements for total coliform 
reduction of < 5% of initial cfu remaining. 

These results indicated that, for this type of contaminant, a 
photochemical system could easily be designed to meet the WHO drinking 
water quality guidelines, which are less stringent than the US EPA 
guidelines. 

Conclusions 

From these studies it was concluded that the use of solar 
photochemical technology has potential for drinking water treatment under 
certain conditions. Specific conclusions are as follows: 

• Ti0 2 photocatalysis is technically feasible for simultaneous 
disinfection and detoxification when the contaminants are well 
identified 



161 

• Dye photosensitization is not an effective treatment for 
simultaneous disinfection and detoxification of aromatic 
hydrocarbons 

• The addition of dye does not enhance the Ti0 2 photocatalytic 
reaction for either disinfection or the destruction of BTEX 

• Ti0 2 photocatalysis in sunlight and under UV light can meet 
WHO drinking water standards for disinfection and BTEX 
destruction 

• Both Ti0 2 photocatalysis and MB photosensitization exhibit 
potential as a small scale disinfectant for rural or peri urban 
applications 

• Photochemical technology may be more appropriate for treatment 
of wastewater or contaminated water, than specifically for 
drinking water. 

Recommendations for Future Work 

The following recommendations are made for future work for 
photochemical technology: 

• Development of inexpensive technology for the separation or 
immobilization of catalyst 

• Testing of the technology on a broader range of both 
microbiological and chemical contaminants, including viruses 

• Determination of relative effectiveness of disinfection techology on 
specific microbiological species 



162 

Exploration of a continuous photochemical supply for 
photosensitization 

Analysis for destruction of sensitizer in photosensitization 

Analysis for intermediate formation in both photocatalysis and 
photosensitization. 






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164 



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2nd ed., Malabar, FL: Krieger Publishing Company, 1992. 

Wolfe, R. L. "Ultraviolet Disinfection of Potable Water." Environmental 
Science and Technology 24 (6 1990): 768-773. 

Wyness, P., J. F. Klausner, D. Y. Goswami and K. S. Schanze. 

"Performance of Nonconcentrating Solar Photocatalytic Oxidations 
REactors Part I: Flat Plate Configuration." Journal of Solar Energy 
Engineering 116 (1 1994): 2-7. 

Zhang, P., R. J. Scrudato and G. Germano. "Solar catalytic Inactivation of 
Escherichia coli in Aqueous Solutions Using Ti0 2 as a Catalyst." 
Chemosphere 28 (3 1994a): 607-611. 

Zhang, Y., J. C. Crittenden and D. W. Hand. "The Solar Photocatalytic 
Decontamination of Water." Chemistry and Industry (19 Sep 1994 
1994b): 714-717. 









APPENDIX A 
EXPERIMENTAL DATA 

Control Reactors, TI02.XLS 





UV Light @ pH 7 




Raw Area 






Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


1 2 


1 


2 


1 


2 


1 


2 


1 


2 


min 


1858.9 


1891.9 


1021.5 


1065.0 


696.2 


743.9 


305.3 


320 1 


351.6 


356.6 


5 min 


1843.7 


1827.4 


1000.3 


1136.4 


568.1 


769.5 


226.1 


327.0 


346.9 


367.8 


15 min 


1958.2 


1789.1 


1062.0 


1113.5 


587.6 


768.8 


239.1 


330.0 


342.4 


343.8 


30 min 


1773.9 


1738.2 


1028.7 


1095.1 


568.7 


796.8 


233.5 


341.4 


346.4 


333.4 


60 min 


1845.9 


1637.5 


1052.7 


1059.1 


5835 


746.2 


233.9 


322.8 


339.9 


329.7 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


1 


2 


1 


2 


1 2 


1 


2 


1 


2 


min 


1839.7 


1891.9 


997.6 


1057.7 


679.9 


743.9 


297.8 


320.1 


342.9 


346.8 


5 min 


1824.5 


1827.4 


976.4 


1129.0 


551.8 


769.5 


218.6 


327.0 


338.2 


358.0 


15 min 


1939.0 


1789.1 


1038.1 


1106.2 


571.2 


768.8 


231.6 


330.0 


333.7 


334.1 


30 min 


1754.7 


1738.2 


1004.7 


1087.7 


552.4 


796.8 


226.1 


341.4 


337.7 


323.6 


60 min 


1826.6 


1637.5 


1028.8 


1051.8 


567.2 


746.2 


226.5 


322.8 


331.2 


319.9 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


1 


2 


1 


2 


1 


2 


1 


2 


1 


2 


min 


5.36 


5.45 


2.91 


3.05 


1.98 


2.14 


0.87 


0.92 


0.1 


0.1 


5 min 


5.39 


5.10 


2.89 


3.15 


1.63 


2.15 


0.65 


0.91 


0.1 


0.1 


15 min 


5.81 


5.36 


3.11 


3.31 


1.71 


2.30 


0.69 


099 


0.1 


0.1 


30 min 


5.20 


5.37 


2.97 


3.36 


1.64 


2.46 


0.67 


1.05 


0.1 


0.1 


60 min 


5.52 


5.12 


3.11 


3.29 


1.71 


2.33 


0.68 


1.01 


0.1 


0.1 




Concentrations 


Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor # 


1 


2 


1 2 


1 


2 


1 


2 


1 


2 


min 


91 6 ppb 


932 ppb 


471 ppb 497 ppb 


303 ppb 


333 ppb 


102 ppb 


1 1 1 ppb 


10 


10 


5 min 


922 ppb 


869 ppb 


467 ppb 


51 6 ppb 


240 ppb 
254 ppb 


334 ppb 
361 ppb 


61 ppb 


110 ppb 


10 


10 


15 min 


997 ppb 


91 4 ppb 


508 ppb 


544 ppb 


70 ppb 


123 ppb 


10 


10 


30 min 


885 ppb 


91 7 ppb 


483 ppb 


553 ppb 


241 ppb 


390 ppb 


66 ppb 


135 ppb 


10 


10 


60 min 


943 ppb 


872 ppb 


507 ppb 


540 ppb 


255 ppb 


367 ppb 


68 ppb 


127 ppb 


10 


10 




Normalized Concentrations 












Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


1 


2 


1 


2 


1 


2 


1 


2 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


1.01 


0.93 


0.99 


1.04 


0.79 


1.00 


0.60 


0.98 






15 min 


1.09 


0.98 


1.08 


1.10 


0.84 


1.09 


0.69 


1.11 






30 min 


0.97 


0.98 


1.03 


1.11 


0.79 


1.17 


064 


1.21 






60 min 


1.03 


0.93 


1.08 


1.09 


0.84 


1.10 


0.67 


1.14 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


0.97 


0.04 


1.01 


0.02 


090 


0.11 


0.79 


0.19 






15 min 

30 min 


1.03 


0.05 


1.09 


0.01 


0.96 


0.12 


0.90 


0.21 






0.98 


0.01 


1 07 


0.04 


0.98 


0.19 


0.93 


0.28 






60 mm 


0.98 


0.05 


1.08 


0.01 


0.97 


0.13 


0.91 


0.23 





























176 



177 



Control Reactors, TI02.XLS 





Dark @ pH 7 






Raw Area 








Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


9 10 


9 


10 


9 


10 


9 


10 


9 


10 


min 


1967.7 


1879.6 


1477.1 


1439.1 


1030.6 


980.1 


408.6 


393.5 


368.0 


339.8 


5 min 


1824.1 


2019.5 


1406.9 


1493.8 


969 9 


1038.2 


392.6 


409.7 


3030 


350.7 


15 min 


1960.0 


1980.5 


1491.7 


1538.1 


1050.5 


1039.3 


419.8 


411.3 


323.0 


340.0 


30 min 


1952.3 


^2002.7 


1505.0 


1526.6 


1041.1 


1016.1 


416.6 


418.7 


335.8 


344.6 


60 min 


1894.8 


2117.4 


1408.9 


1585.4 


1031.0 


1050.3 


417.2 


431.8 


327.4 


324.2 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


9 


10 


9 


10 


9 


10 


9 


10 


9 


10 


Omin 


1938.0 


1850.0 


1435.4 


1397.4 


999.8 


949.3 


394.7 


379.6 


360.7 


332.57 


5 min 


1794.5 


1989.8 


1365.2 


1452.1 


939.1 


1007.5 


378.7 


395.8 


295.8 


343.44 


15 min 


1930.4 


1950.8 


1449 9 


1496.4 


1019.7 


1008.5 


406.0 


397.4 


315.7 


332.78 


30 min 


1922.6 


1973.0 


1463.2 


1484.8 


1010.3 


985.3 


402.7 


404.8 


328.5 


337.39 


60 min 


1865.1 


2087.8 


1367.1 


1543.7 


1000.2 


1019.5 


403.3 


417.9 


320.2 


317.01 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


9 


10 


9 


10 


9 


10 


9 


10 


9 


10 


min 


5.37 


5.56 


3.98 


4.20 


2.77 


2.85 


1.09 


1.14 


0.1 


0.1 


5 min 


6.07 


5.79 


4.62 


4.23 


3.18 


2.93 


1.28 


1.15 


0.1 


0.1 


15 min 


6.11 


5.86 


4.59 


4.50 


3.23 


303 


1.29 


1.19 


0.1 


0.1 


30 min 


5.85 


5.85 


4.45 


440 


3.08 


2.92 


1.23 


1.20 


0.1 


0.1 


60 min 


5.83 


6.59 


4.27 


4.87 


3.12 


3.22 


1.26 


1.32 


0.1 


0.1 




Concentrations 






Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor # 


9 


10 


9 10 


9 


10 


9 


10 


9 


10 


min 


91 8 ppb 


952 ppb 


665 ppb 705 ppb 


446 ppb 


461 ppb 


143 ppb 


151 ppb 


10 


10 


5 min 


1043 ppb 


994 ppb 
1006 ppb 


780 ppb 


710 ppb 


520 ppb 


476 ppb 


176 ppb 


153 ppb 


10 


10 


15 min 


1052 ppb 


776 ppb 


759 ppb 


529 ppb 


493 ppb 


177 ppb 


161 ppb 


10 


10 


30 min 


1004j>pb 


1004 ppb 


751 ppb 


742 ppb 


501 ppb 


473 ppb 


166 ppb 


162 ppb 


10 


10 


60 min 


1000 ppb 


11 37 ppb 


71 8 ppb 


826 ppb 


510 ppb 


527 ppb 


172 ppb 


183 ppb 


10 


10 






Normalized Concentrations 












Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


9 


10 


9 


10 


9 


10 


9 


10 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


1.14 


1.04 


1.17 


1.01 


1.16 


1.03 


1.24 


1.01 






15 min 


1.15 


1.06 


1.17 


1.08 


1.19 


1.07 


1.24 


1.06 






30 min 


1.09 


1.05 


1.13 


1.05 


1.12 


1.03 


1.17 


1.07 






60 mm 


1.09 


1.19 


1.08 


1.17 


1.14 


1.14 


1.21 


1.21 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


1.09 


0.05 


1.09 


0.08 


1.10 


0.07 


1.12 


0.11 






15 min 


1.10 


0.04 


1.12 


0.05 


1.13 


0.06 


1.15 


0.09 






30 min 


1.07 


0.02 


1.09 


0.04 


1.07 


0.05 


1.12 


0.05 






60 mm 


1.14 


0.05 


1.13 


0.05 


1.14 


0.00 


1.21 


0.00 







178 






Control Reactors, TI02.XLS 







UV Light @ pH 4 












Raw Area 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


77 


18 


17 


18 


17 


18 


17 


18 


17 


18 


min 


1506.97 


1502.08 


976.19 


982.82 


469.28 


470.8 


193.61 


200.3 


329.9 


334.69 


5 min 


1590.08 


1595.19 


996 3 


1055.99 


461.4 


491.82 


196.22 


207.15 


314.97 


351.29 


15 min 


1623.54 


1591.84 


1037.26 


1034.55 


503.98 


493.19 


209.46 


213.34 


325.83 


336.04 


30 min 


1574.43 


1461.74 


1054.33 


1025.17 


506.8 


544.7 


217.5 


234.87 


330.41 


336.48 


60 min 


306.95 


1546.92 


238.43 


1126.6 


136.81 


621.13 


81.34 


264.22 


388.04 


357.93 




Adjusted 












Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


17 


18 


17 


18 


17 


18 


17 


18 


17 


18 


5 min 


1590.08 


1595.19 


996.3 


yo/.oz 
1055.99 


469.28 
461.4 


470.8 
491.82 


193.61 
196.22 


200.3 
207.15 


329.9 
314.97 


334.69 
351.29 


15 min 


1623.54 


1591.84 


1037.26 


1034.55 


503.98 


493.19 


209.46 


213.34 


325.83 


336.04 


30 min 


1574.43 


1461.74 


1054.33 


1025.17 


506.8 


544.7 


217.5 


234.87 


330.41 


336.48 


60 min 


306.95 


1546.92 


238.43 


1126.6 


136.81 


621.13 


81.34 


264.22 


388.04 


357.93 






Referenced 






Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


17 


18 


17 


18 


17 


18 


17 


18 


17 


18 


Omin 


4.57 


4.49 


2.96 


2.94 


1.42 


1.41 


0.59 


0.60 


0.1 


0.1 


5 min 


5.05 


4.54 


3.16 


3.01 


1.46 


1.40 


0.62 


059 


0.1 


0.1 


15 min 


4.98 


4.74 


3.18 


3.08 


1.55 


1.47 


0.64 


0.63 


0.1 


0.1 


30 min 


4.77 


4 34 


3.19 


3.05 


1.53 


1.62 


0.66 


0.70 


0.1 


0.1 


60 min 


0.79 


4.32 


0.61 


3.15 


0.35 


1.74 


0.21 


0.74 


0.5 


0.1 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor # 


17 


18 


17 


18 


17 


18 


17 


18 


17 


18 


Omin 


772 ppb 


757 ppb 


480 ppb 


476 ppb 


202 ppb 


199 ppb 


51 ppb 


53 ppb 


10 


10 


5 min 


859 ppb 


767 ppb 


517 ppb 


489 ppb 


210 ppb 


198 ppb 


57 ppb 


51 ppb 


10 


10 


15 min 


847 ppb 


802 ppb 


521 ppb 


502 ppb 


225 ppb 


210 ppb 


61 ppb 


59 ppb 


10 


10 


30 min 


808 ppb 


731 ppb 


522 ppb 


496 ppb 


222 ppb 


238 ppb 


64 ppb 


71 ppb 


10 


10 


60 mm 


18 ppb 


727 ppb 


11 ppb 


51 4 ppb 


2 ppb 


259 ppb 


1 ppb 


78 ppb 


2 


10 






Normalized C< 


incentration 


s 












Benzene 


Toluene 


m&p-) 


ylene 


o-xylene 






Reactor it 


17 


18 


17 


18 


17 


18 


17 


18 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


1.11 


1.01 


1.08 


1.03 


1.04 


0.99 


1.13 


0.97 






15 min 


1.10 


1.06 


1.08 


1.05 


1.11 


1.06 


1.20 


1.13 






30 min 


1.05 


0.97 


1.09 


1.04 


1.10 


1.19 


1.26 


1.34 






60 min 


0.02 


0.96 


0.02 


1.08 


0.01 


1.30 


0.02 


1.48 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






Omin 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


1.06 


0.05 


1 05 


003 


1.02 


0.02 


1.05 


0.08 






15 mm 


1.08 


0.02 


1.07 


0.02 


1.08 


0.03 


1.16 


04 






30 min 


1.01 


0.04 


1.06 


002 


1.15 


0.05 


1.30 


0.04 






60 min 


0.49 


0.47 


0.55 


0.53 


0.65 


0.65 


0.75 


0.73 






























179 



Control Reactors, TI02.XLS 





Dark @ pH 4 






Raw Area 








Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


25 


26 


25 


26 


25 


26 


25 


26 


25 


26 


min 


1834.74 


2089.47 


1512.20 


1752.57 


981.57 


1107.61 


390.90 


463.79 


363.74 


359.02 


5 min 


1935.79 


2213.77 


1716.51 


1888.85 


1099.80 


1207.84 


453.91 


506.12 


358.09 


346.97 


15 min 


1910.17 


1883.61 


1694.00 


1640.92 


1081.81 


1090.52 


443.65 


454.70 


357.63 


363.31 


30 min 


1857.45 


1758.63 


1630.87 


1537.70 


1071.19 


994.99 


442.80 


414.41 


374.89 


359.73 


60 min 


1889.55 


1917.40 


1673.64 


1633.89 


1058.40 


1027.93 


439.43 


434.51 


371.12 


359.43 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


25 


26 


25 


26 


25 


26 


25 


26 


25 


26 


min 


1778.48 


2033.21 


1425.86 


1666.23 


910.12 


1036.16 


355.13 


428.02 


355.52 


350.80 


5 min 


1879.53 


2157.51 


1630.17 


1802.51 


1028 35 


1136.39 


418.14 


470.35 


349.87 


338.75 


15 min 


1853.91 


1827.35 


1607.66 


1554.58 


1010.36 


1019.07 


407.88 


418.93 


349.41 


355.09 


30 min 


1801.19 


1702.37 


1544.53 


1451.36 


999.74 


923.54 


407.03 


378.64 


366.67 


351.51 


60 min 


1833 29 


1861.14 


1587.30 


1547.55 


986.95 I 956.48 


403.66 


398.74 


362.90 


351.21 






Referenced 






Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor » 


25 


26 


25 


26 


25 


26 


25 


26 


25 


26 


min 


5.00 


5.80 


4.01 


4.75 


2.56 


2.95 


1.00 


1.22 


0.1 


0.1 


5 min 


5.37 


637 


4.66 


5.32 


2.94 


3.35 


1.20 


1.39 


0.1 


0.1 


15 mm 


5.31 


5.15 


460 


4 38 


2.89 


2.87 


1.17 


1.18 


0.1 


0.1 


30 min 


4.91 


4.84 


4.21 


4.13 


2.73 


2.63 


1.11 


1.08 


0.1 


0.1 


60 min 


5.05 


5.30 


4.37 


4.41 


2.72 


2.72 


1.11 


1.14 


0.1 


0.1 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor* 


25 


26 


25 


26 


25 


26 


25 


26 


25 


26 


Omin 


851jjpb 


994 ppb 


671 ppb j 805 ppb 


408 ppb 


479jy>b 


125 ppb 


165 ppb 


10 


10 


5 mm 


917ppb j 


1098 ppb 


788 ppb 


908 ppb 


477 ppb 


552 ppb 


161 ppb 


196 ppb 


10 


10 


15 min 


905 ppb 


877 ppb 


778 ppb 


737 ppb 


468 ppb 


464 ppb 


156 ppb 


158 ppb 


10 


10 


30 min 


834 ppb 


822 ppb 


707 ppb 


692 ppb 


438 ppb 


420 ppb 


145 ppb 


139 ppb 


10 


10 


60 min 


859 ppb | 904 ppb 


737 ppb 


743 ppb 


437 ppb 


438 ppb 


146 ppb 


150 ppb 


10 


10 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


25 


26 


25 


26 


25 


26 


25 


26 






Omin 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


1.08 


1.10 


1.18 


1.13 


1.17 


1.15 


1.28 


1.18 






15 min 


1.06 


0.88 


1.16 


0.92 


1.15 


0.97 


1.24 


0.96 






30 min 


0.98 


0.83 


1.05 


0.86 


1.07 


0.88 


1.16 


0.84 






60 min 


1.01 


0.91 


1.10 


0.92 


1.07 


91 


1.16 


091 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


1.09 


0.01 


1.15 


0.02 


1.16 


0.01 


1.23 


0.05 






15 min 


0.97 


0.09 


1.04 


0.12 


1.06 


0.09 


1.10 


0.14 






30 min 

60 min 


0.90 
0.96 


0.08 
0.05 


0.96 
1.01 


0.10 
0.09 


0.98 
0.99 


0.10 
0.08 


1.00 
1.04 


0.16 

13 







180 



0.01% Ti02, TI02.XLS 









UV Ligh 

Area 


t@pH7 












Raw 












Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


3 


4 


3 


4 


3 


4 


3 


4 


3 


4 


Omin 


1733.8 


1874.1 


975.3 


1013.4 


497.4 


529.0 


208.5 


211.4 


321.8 


342.87 


5 min 


1647.1 


1395.2 


855.7 


751.7 


417.2 


380.6 


159.6 


154.9 


334.2 


334.93 


15 min 


751.6 


688.1 


367.8 


349.6 


179.0 


177.6 


68.8 


69.1 


290.1 


319.29 


30 min 


445.7 


455.6 


214.4 


219.3 


99.3 


105.0 


35.8 


38.5 


276.8 


334.1 


60 min 


80.6 


78.5 


43.1 


43.9 


23.7 


22.7 


10.0 


0.0 


308.5 


295.27 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


3 


4 


3 


4 


3 


4 


3 


4 


3 


4 


min 


1733.8 


1874.1 


968.0 


1006.1 


497.4 


529.0 


208.5 


211.4 


312.0 


333.095 


5 min 


1647.1 


1395.2 


848.4 


744.3 


417.2 


380.6 


159.6 


154.9 


324.4 


325.155 


15 min 


751.6 


688.1 


360.4 


342.3 


179.0 


177.6 


68.8 


69.1 


280.3 


309.515 


30 mm 


445.7 


455.6 


207.1 


212.0 


99.3 


105.0 


35.8 


38.5 


267.0 


324.325 


60 min 


80.6 


78.5 


35.8 


36 6 


23.7 


22.7 


100 


0.0 


298.8 


285.495 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor It 


3 


4 


3 


4 


3 


4 


3 


4 


3 


4 


min 


5.56 


5.63 


310 


3.02 


1.59 


1.59 


0.67 


0.63 


10 


0.10 


5 min 


5.08 


4.29 


2.62 


2 29 


1.29 


1.17 


0.49 


0.48 


0.30 


0.30 


15 min 


2.68 


2.22 


1.29 


1.11 


0.64 


0.57 


0.25 


0.22 


0.50 


0.50 


30 min 


1.67 


1.40 


0.78 


0.65 


0.37 


0.32 


0.13 


0.12 


0.98 


1.00 


60 min 


0.27 


0.28 


0.12 


0.13 


0.08 


0.08 


0.03 


0.00 


0.98 


1.00 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor it 


3 


4 


3 


4 


3 


4 


3 


4 


3 


4 


Omin 


951 ppb_ 
288 ppb 


964 ppb 


506 ppb 


491 ppb 


233 ppb 


232 ppb 
52 ppb 


65 ppb 


59 ppb 


10.00 


10.00 


5 mm 


241 ppb 


139 ppb 


120 ppb 


59 ppb 


11 ppb 


10 ppb 


3.33 


3.33 


15 min 


86 ppb 


69 ppb 


35 ppb 


29 ppb 


12 ppb 


10 ppb 


1 ppb 


1 ppb 


2.00 


2.00 


30 min 


25 ppb 


20 ppb 


9 ppb 


6 ppb 


1 ppb 


Oppb 


1 ppb 


1 ppb 


1.02 


1.00 


60 mm 


1 PPb 


1 ppb 


1 ppb 


1 ppb 


1 ppb 


1 ppb 


1 ppb 


Oppb 


1.02 


1.00 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


3 


4 


3 


4 


3 


4 


3 


4 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


0.30 


0.25 


0.28 


0.24 


0.25 


0.22 


0.17 


0.17 






15 min 


0.09 


0.07 


0.07 


0.06 


0.05 


0.04 


0.02 


0.02 






30 mm 


0.03 


0.02 


0.02 


0.01 


0.01 


0.00 


0.02 


0.02 






60 min 


0.00 


0.00 


0.00 


000 


0.00 


0.00 


0.02 


0.00 








Statistics 










Benzene 


Toluene 


m&p-> 


ylene 


o-xylene 








Ava 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


0.28 


0.03 


0.26 


002 


0.24 


0.01 


0.17 


0.00 






15 min 


0.08 


0.01 


0.06 


0.01 


0.05 


0.00 


0.02 


0.00 






30 min 


0.02 


0.00 


0.01 


000 


0.00 


0.00 


0.02 


0.00 


AvdSD 


0.0047 


60 min 


0.00 


0.00 


0.00 


0.00 


0.00 


0.00 


0.01 


0.01 





























181 



0.01% Ti02. TI02.XLS 



Reactor it 



min 



5 min 

15 min 
30 min 



60 min 



Reactor it 



min 

5 min 

15 min 

30 min 

60 min 



Re actor tt 

min 

5 min 

15 min 



30 min 



60 min 



Reactor tt 



min 



Benzene 



11 



12 



1979.7 



21 53.9 



1966.9 



2080.6 



2066.3 



2142.3 



1920.1 



2059.5 



1976.1 



2104 4 



Raw Area 



Dark@pH7 



Toluene 



11 



1497 2 



1485.4 



1505.3 



1423.4 



1498.0 



12 



1614.6 



1601.8 



1624.3 



1607.6 



1596.0 



m& p-xylene 



11 



1014.5 



1014.2 



992.9 



981.9 



1025.6 



Benzene 



11 



12 



2009.3 
1996.5 



2176.0 



2102.6 



2095.9 



2164.3 



1949.8 
2005.7 



2081 6 



2126.4 



Toluene 



Adjusted 



12 



1099.9 



1068.6 



1113.1 



1068.5 



1075.4 



11 



o-xylene 



403.9 



403.7 



408.5 



396.3 



412.3 



11 



1538.9 



1527.2 



1547.0 



1465.1 



1539.7 



12 



1642.8 



1630.1 



1652.5 



1635.9 



1624.2 



m&p-xylene 



11 



1045.3 



1045.0 



1023.7 



J0 127 
1056.4 



Benzene 



Referenced 



12 



1128.8 



1097.5 



1142.0 



1097.3 



1104.2 



12 



431.9 



430.5 



449.6 



430.7 



433.2 



11 



o-xylene 



417.8 



417.6 



422.4 



410.1 



426.2 



Toluene 



11 



12 



11 



5.98 



578 



4.58 



6.29 
6.23 



6.13 



4.81 



6.00 



4.60 



5.91 



5.92 



4.44 



5.50 



6.26 



4.23 



12 



4.36 



4.75 



4.58 



4.66 



4.78 



m&p - xylene 



11 



3.11 



3.29 



3.04 



3.07 



Benzene 



11 



Toluene 



Concentrations 



2.90 



12 



3.00 



3.20 



3.16 



3.12 



3.25 



12 



445.5 



444.0 



463.2 



444.3 



446.7 



Chlorobenzene 



JJ 

328.8 



310.4 



329.3 



322.6 



357.2 



12 



369.7 



335.9 



353.9 



344.4 



332.7 



Chlorobenzene 



11 



336.0 



317.6 



336.5 



329.8 



11 



o-xylene 



1.24 



1.31 



1.26 



1.24 



1.17 



12 



11 



5 min 
15 min 
30 min 
60 min 



1028 p pb 



1083 ppb 
1073 ppb 



991 ppb 



1055 ppb 



1015 ppb 



1031 ppb 



774 ppb 
81 5 ppb 



941 pp b 



1017 ppb 



1078 ppb 



J777pjb_ 
749 ppb 



710 ppb 



12 



734 ppb 



805 ppb 
774 p pb 



788 p pb 



81 1 ppb 



m&p- x ylene 



11 



508 ppb 



540 p pb 



495 ppb 



501 ppb 
46 9 ppb 



12 



487 ppb 



524 ppb 



51 8 ppb 



51 ppb 



Benzene 



Normalized C oncentrations 



533 ppb 



12 



1.18 



1.29 



1.28 



1.26 



1.32 



11 



o-xylene 



170 ppb 



183 ppb 



1 72 ppb 



170 ppb 



156 ppb 



Reactor it 



11 



12 



Toluene 



11 



min 

5 min 

15 min 

30 min 

60 min 



1.00 



1.00 



1.00 



1.05 
1.04 
0.99 
0.92 



1.07 



1.05 



1.04 



1.00 



1.03 



0.97 



1.09 



0.92 



12 



1.00 



1.10 



1.05 



1.07 



1.10 



11 



m &p-xylene 



1.00 



1.06 



0.98 



0.99 



0.92 



min 

5 min 

15 min 

30 min 

60 min 



Avq 



Benzene 



SD 



1.00 

1.06 
1.04 
1.01 " 
1.00 



0.00 
0.01 
0.00 

_ap2 

0.09 



Avq 



Toluene 



Statistics 



12 



1.00 



1.08 



1.06 



1.05 



1.09 



12 



158 ppb 



179 ppb 



177 ppb 



173 ppb 



1 83 ppb 



364.4 



12 



376.8 



342.9 



360.9 



351. 



339.7 



Sample 



Dilution 



11 



0.1 



0.1 



0.1 



0.1 



0.1 



12 



0.1 



0.1 



0.1 



0.1 



0.1 



Dilution 



Factor 



11 



10 



10 



10 



12 



10 



10 



10 



11 



o-xylene 



1.00 



1.08 



1.01 



1.00 



0.92 



SD 



1.00 
1.08 
y)3 
1.02 

1.01 



0.02 

JLQ3 

0J35 
0.09 



m&p-xylene 



Avq 



SD 



1.00 

1.07 
1J32 
1.02 

1.01 



CK50 
0.01 
0.04 

0.03 
0.09 



12 



1.00 



1.13 



1.12 



1.09 



1.15 



Avq 



o-xylene 



SD 



1.00 
1.10 
1.06 
1.05 
1.04 



0.00 
0.03 
0.05 
0.05 
0.12 



10 



10 



JO 
10 



AvdSD 



0.0356 



182 









0.01% Ti02, TI02.XLS 





UV Light @ pH 4 






Raw Area 








Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


19 


20 


19 


20 


19 20 


19 20 


19 


20 


min 


1448.44 


1583.69 


987.85 


1077.18 


451.56 484.74 


191.46 


203.69 


339.72 


348.18 


5 min 


2145.27 


3114.01 


1416.17 


2073.28 


611.66 997.62 


277.65 


419.74 


323.47 


341.71 


15 min 


1733.81 


1638.23 


1081.52 


1062.7 


511.57 518.21 


202.06 


213.02 


293.28 


322.49 


30 min 


869.28 


754.57 


494.9 


47881 


237.25 217.29 


95.79 


88 98 


325.44 


295.32 


60 min 


120.98 


188.52 


76.94 


114.88 


36.51 54.39 


14.59 


21.29 


238.02 


290.98 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


19 


20 


19 


20 


19 


20 


19 20 


19 20 


min 


1448.44 


1563.39 


987.85 


1056.29 


451.56 


472.095 


191.46 


197.825 


339.72 


335.535 


5 min 


2145.27 


3093.71 


1416.17 


2052.39 


61 1 .66 


984.975 


277.65 


413.875 


323.47 


329.065 


15 min 


1733.81 


1617.93 


1081.52 


1041.81 


511.57 


505.565 
204.645 


202.06 


207.155 


293.28 


309.845 


30 min 


869.28 


734.27 


494.9 


457.92 


237.25 


95.79 


83.115 


325.44 


282.675 


60 min 


120.98 


16822 


76.94 


93 99 


36.51 


41 .745 


14.59 


15.425 


238.02 


278.335 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor * 


19 


20 


19 


20 


19 


20 


19 


20 


19 


20 


min 


4.26 


4.66 


2.91 


3.15 


1.33 


1.41 


0.56 


0.59 


0.1 


0.1 


5 min 


6.63 


9.40 


4.38 


6.24 


1.89 


2.99 


0.86 


1.26 


0.3 


0.3 


15 min 


591 


5.22 


3.69 


3.36 


1.74 


1.63 


0.69 


0.67 


05 


0.3 


30 min 


2.67 


2.60 


1.52 


1.62 


0.73 


0.72 


0.29 


0.29 


0.98 


05 


60 min 


0.51 


0.60 


0.32 0.34 


0.15 


015 


0.06 


0.06 


0.98 


0.98 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor # 


19 


20 


19 


20 


19 


20 


19 


20 


19 


20 


min 


717ppb 


788 ppb 


471 ppb 


51 5 ppb 


185 ppb 


199 ppb 


46 ppb 


51 ppb 


10.00 


10.00 


5 min 


382 ppb 


549 ppb 


246 ppb 


358 ppb 


96 ppb 


162 ppb 


33 ppb 


57 ppb 


3.33 


3.33 


15 min 


203 ppb 


297 ppb 


122 ppb 


184 ppb 


52 ppb 


80 ppb 


14 ppb 


22 ppb 


200 


3.33 


30 mm 


44 ppb 


83 ppb 


22 ppb 


48 ppb 


8 ppb 


15 ppb 


1 PPb 


1 ppb 


1.02 


2.00 


60 min 


4 ppb 


5 ppb 


Oppb 


1 ppb 


1 ppb 


1 PPb 


1 ppb 


1 ppb 


1.02 


1.02 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


19 


20 


19 


20 


19 


20 


19 20 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


0.53 


0.70 


0.52 


0.70 


0.52 


0.81 


0.72 


1.12 






15 min 


0.28 


0.38 


0.26 


0.36 


0.28 


0.40 


0.30 


0.43 






30 min 


0.06 


0.11 


0.05 


0.09 


0.04 


0.08 


0.02 


0.02 






60 min 


0.01 


0.01 


000 


0.00 


0.01 


0.01 


0.02 


0.02 










Statistics 












Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avq 


SD 


Avq 


SD 


Avg 


SD 






min 


1.00 


000 


1.00 


0.00 


1 00 


0.00 


1.00 


0.00 






5 min 


0.61 


0.08 


0.61 


0.09 


0.67 


0.15 


0.92 


0.20 






15 min 


0.33 


0.05 


0.31 


0.05 


0.34 


0.06 


0.36 


0.06 






30 min 


0.08 


0.02 


0.07 


0.02 


0.06 


0.02 


0.02 


0.00 


AvdSD 


0.0403 


60 min 


0.01 


0.00 


000 


0.00 


0.01 


0.00 


0.02 


0.00 































183 



0.01% Ti02, TI02.XLS 





Dark @ pH 4 






Raw Area 








Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


27 28 


27 


28 


27 28 


27 28 


27 


28 


min 


1832.27 


1732.28 


1617.83 


1540.56 


1052.36 
969.51 


99291 


424.93 


408.18 


339.32 


365.11 


5 min 


1720.36 


1844.29 


1506.01 


1635 55 


1061.41 


409 96 


452.17 


346.64 


361.75 


15 min 


566.18 


1837.19 


444.72 


1690 27 


286.89 1066.18 


129.3 


452.59 


351.5 


341.46 


30 min 


4427.07 


1620.28 


3920.01 
3646.46 


1469.56 


2548.8 1 926.62 


1068.19 


398.23 


359.88 


365.47 


60 mm 


4205.84 


1746.93 


1505.29 


2501.18 1028.34 


1049.85 


422.13 


359.17 


353.38 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


27 


28 


27 


28 


27 


28 


27 


28 


27 


28 


min 


1888.54 


1749.70 


1704.17 


1566.75 


1123.82 


1017.22 


460.70 


420 94 


347.55 


373.88 


5 min 


1776.63 


1861.71 


1592.35 


1661.74 


1040.97 


1085.72 


445.73 


464.93 


354.87 


370.52 


15 min 


622.45 


1854.61 


531 .06 


1716.46 


358.35 


1090.49 


165.07 


465.35 


359.73 


35023 


30 min 


4483.34 


1637.70 


4006.35 


1495 75 


2620.26 


950.93 


1103.96 


410.99 


368.11 


374.24 


60 min 


4262.11 


1764.35 


3732.80 


1531.48 


2572.64 


1052.65 


1085.62 


434.89 


367.40 


362.15 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


27 


28 


27 


28 


27 


28 


27 


28 


27 


28 


min 


5.43 


4.68 


4.90 


419 


3.23 


2.72 


1.33 


1.13 


01 


0.1 


5 min 


5.01 


5.02 


4.49 


4.48 


2.93 


2.93 


1.26 


1.25 


0.1 


0.1 


15 min 


1.73 


5.30 


1.48 


4.90 


1.00 


3 11 


046 


1.33 


0.1 


0.1 


30 min 


1218 


4.38 


10.88 


4.00 


7.12 


2.54 


300 


1.10 


0.3 


0.1 


60 min 


11.60 


4.87 


1016 


4.23 


7.00 


2.91 


2.95 


1.20 


0.3 


0.1 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor M 


27 


28 


27 28 


27 


28 


27 28 


27 


28 


min 


929 ppb 


792 ppb 


833 ppb 703 ppb 


530 ppb 
476 ppb 


437 ppb 
475 ppb 


1 84 ppb 


148 ppb 


10 


10 


5 min 


851 ppb 


855 ppb 


757 ppb 


757 ppb 


172 ppb 


172 ppb 


10 


10 


15 min 


258 ppb 


904 ppb 


21 2 ppb 


832 ppb 


125 ppb 


508 ppb 


27 ppb 


185 ppb 


10 


10 


30 min 


71 7 ppb 


737 ppb 


639 ppb 


668 ppb 


41 1 ppb 


405 ppb 


163 ppb 


143 ppb 


3.333333 


10 


60 min 


682 ppb 


827 ppb 


595 ppb 


71 ppb 


404 ppb 


471 ppb 


160 ppb 


162 ppb 


3.333333 


10 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor It 


27 


28 


27 


28 


27 


28 


27 


28 






mm 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


0.92 


1.08 


0.91 


1.08 


0.90 


1.09 


0.93 


1.16 






15 min 


0.28 


1.14 


0.25 


1.18 


0.24 


1.16 


0.15 


1.25 






30 min 


0.77 


0.93 


0.77 


0.95 


0.78 


0.93 


0.88 


0.97 






60 min 


0.73 


1.04 


0.71 


1.01 


0.76 


1 08 


0.87 


1.09 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1 00 


0.00 


1.00 


0.00 






5 min 


1.00 


0.08 


0.99 


0.08 


99 


0.09 


1.04 


0.11 






15 min 


0.71 


0.43 


0.72 


0.46 


070 


0.46 


0.70 


0.55 






30 min 


0.85 


08 


0.86 
0.86 


0.09 


0.85 
0.92 


0.07 


0.92 


0.04 


AvdSD 


0.1571 


60 min 


0.89 0.15 


0.15 


0.16 


0.98 


0.11 










184 






0.05% Ti02. TI02.XLS 








UV Light @ pH 7 






Raw Area 








Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


5 


6 


5 


6 


5 


6 


5 


6 


5 


6 


min 


1703.09 


1984.40 


966.07 


1093.10 


499.36 


562.34 


204.64 


222.76 


295.62 


354.80 


5min 


2883.61 


1925.68 


1624.48 


1056.15 


877.49 


557.20 


355.76 


221 .56 


331 .78 


358.91 


15 min 


4303.10 


1649.94 


2385.48 


928.49 


1316.55 


489.98 


526.35 


197.31 


331.19 


348.73 


30 min 


5196.38 


1131.51 


3145.22 


636.48 


1649.49 


320.56 


644 42 


127.38 


277.81 


329.68 


60 min 


1957.67 


3001.18 


1032.92 


1679.48 


545.74 


845.64 


331.52 


336.54 


358.78 


320.58 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


5 


6 


5 


6 


5 


6 


5 


6 


5 


6 


min 


1735.04 


2016.35 


994.69 


1121.72 


520.18 


583.16 


214.16 


232.28 


30296 


362.14 


5 min 


2915.56 


1957.63 
1681.89 


1653.10 


1084.77 


898.31 


578.02 


365.28 


231 .08 


339.12 


366.25 


15 min 


4335.05 
5228.33 
1989.62 


2414.10 


957.11 


1337.37 


510.80 


535.87 


206.83 


338.53 


356.07 


30 min 


1163.46 


3173.84 


665.10 


1670.31 


341.38 


653.94 


136.90 


285.15 


337.02 


60 min 


3033.13 


1061.54 


1708.10 


566.56 


866 46 


341.04 


346.06 


366.12 


327.92 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


5 


6 


5 6 


5 


6 


5 


6 


5 


6 


Omin 


5.73 


5.57 


3.28 


3.10 


1.72 


1.61 


0.71 


0.64 


0.1 


0.1 


5 min 


8.60 


5.35 


4.87 


2.96 


2.65 


1 58 


1.08 


0.63 


0.3 


0.1 


15 min 


12.81 


4.72 


7.13 


2.69 


3.95 


1.43 


1.58 


0.58 


0.5 


0.1 


30 min 


18.34 


3.45 


11.13 


1.97 


5.86 


1.01 


2.29 


0.41 


1 


0.1 


60 min 


5.43 


9.25 


2.90 


5.21 


1.55 


2.64 


0.93 


1.06 


0.5 


0.5 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor It 


5 


6 


5 


6 


5 6 


5 


6 


5 


6 


min 


982 ppb 


953 ppb 


539 ppb 


505 ppb 


255 ppb 236 ppb 


72 ppb 


60 ppb 


10.0 


10 


5 min 


501 ppb 


91 3 ppb 


276 ppb 


481 ppb 


141 ppb 


230 ppb 


46 ppb 


59 ppb 


3.3 


10 


15 min 


453 ppb 


800 ppb 


247 ppb 


431 ppb 


132 ppb 


204 ppb 


46 ppb 


50 ppb 


2.0 


10 


30 min 


327pj>b 


570 ppb 


196 ppb 


302 ppb 


101 ppb 


128 ppb 


36 ppb 


18 ppb 


1.0 


10 


60 min 


186 ppb 


324 ppb 


94 ppb 


178 ppb 


45 ppb 


85 ppb 


23 ppb 


27 ppb 


2.0 


2 




Normalized Concentrations 










Benzene 


Toluene 


m&p-> 


cylene 


o-xylene 






Reactor it 


5 


6 


5 


6 


5 


6 


5 


6 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


0.51 


0.96 


0.51 


0.95 


0.55 


0.98 


0.64 


0.97 






15 min 


0.46 


084 


0.46 


0.85 


0.52 


0.87 


0.64 


0.82 






30 min 


33 


0.60 


0.36 


0.60 


0.39 


0.54 


0.50 


0.30 






60 min 


0.19 


0.34 


0.17 


0.35 


0.18 


0.36 


0.31 


0.45 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


0.73 


0.22 


0.73 


0.22 


0.76 


0.21 


0.81 


0.16 






15 min 


0.65 


0.19 


0.66 


0.20 


0.69 


0.17 


0.73 


0.09 






30 min 


0.47 


0.13 


0.48 


0.12 


0.47 


0.07 


0.40 


0.10 






60 min 


0.26 


0.08 


0.26 


0.09 


0.27 


0.09 


0.38 


0.07 





























185 



0.05% Ti02, TI02.XLS 





Dark @ pH 7 








Raw Area 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor It 


13 


14 


13 


14 


13 


14 


13 


14 


13 


14 


min 


2063.2 


2249.1 


1550.4 


16486 


1106.5 


1173.3 


443.2 


468.7 


325.27 


381.62 


5 min 


2180.9 


2161 7 


1624.5 


1583.8 


1149.1 


1122.7 


459.8 


453.3 


339.40 


352.98 


15 min 


2137.0 


2255.0 


1586.3 


1724.5 


1120.4 


1223.9 


4524 


484.4 


320.88 


355.44 


30 min 


2159.5 


2299.6 


1627.6 


1735.5 


1150.4 


1210.6 


462.4 


482.5 


338.81 


360.49 


60 min 


2210.1 


2097.3 


1621.8 


1642 2 


1180.0 


11179 


475 5 


447.8 


350.25 


332.81 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


13 


14 


13 


14 


13 


14 


13 


14 


73 


14 


min 


2085.3 


227\.\ 


15786 


1676.9 


1135.3 


1202.2 


456.8 


482.3 


332.29 


388.64 


5 min 


2202.9 


2183.8 


1652.7 


1612.1 


1178.0 


1151.6 


473.4 


466.9 


346.42 


360.00 


15 min 


2159.1 


2277.0 


1614.5 


1752.7 


1149.2 


1252.8 


466.0 


498.0 


327.90 


362.46 


30 min 


2181.6 


2321 .7 


1655.9 


1763.8 


1179.3 


1239.5 


475.9 


496.1 


345.83 


367.51 


60 min 


2232.2 


21194 


1650.0 


1670.4 


1208.9 


1146.8 


489.0 


461.3 


357.27 


339.83 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor tt 


13 


14 


13 


14 


73 


14 


13 


14 


13 


14 


Omin 


6.28 


5.84 


4.75 


4.31 


3.42 


3.09 


1.37 


1.24 


0.1 


0.1 


5 min 


6 36 


6.07 


4.77 


4.48 


3.40 


3.20 


1.37 


1.30 


0.1 


0.1 


15 min 


6.58 


6.28 


4.92 


4.84 


3.50 


3.46 


1.42 


1.37 


0.1 


0.1 


30 min 


6.31 


6.32 


4.79 


4.80 


3.41 


3.37 


1.38 


1.35 


0.1 


0.1 


60 min 


6.25 


6.24 


4.62 


4.92 


3.38 


3.37 


1.37 


1.36 


0.1 


0.1 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor # 


13 


14 


13 14 


13 


14 


13 14 


13 


14 


min 


1081 ppb 


1003 ppb 


805 ppb j 726 ppb 


563 ppb 
560 ppb 


505 ppb 
" 524 ppb 


193 ppb 


169 ppb 


10 


10 


5 min 


1096 ppb 
1137 ppb 


1043 ppb 
1082 ppb 


809 ppb 756 ppb 


192 ppb 


179 ppb 


10 


10 


15 min 


836 ppb 820 ppb 


579 ppb 
562 ppb 
557 ppb 


570 ppb 
555 ppb 


202 ppb 


193 ppb 


10 


10 


30 min 


1087 ppb 


1 089 ppb 


81 2 ppb 


814 ppb 
835 ppb 


194 ppb 


189 ppb 


10 


10 


60 min 


1076 ppb 


1074 ppb 


781 ppb 


556 ppb 


192 ppb 


190 ppb 


10 


10 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


13 


14 


13 


14 


13 


14 


13 


14 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1 00 


1.00 


1.00 






5 min 


1.01 


1.04 


1.00 


1.04 


0.99 


1.04 


0.99 


1.06 






15 min 


1.05 


1.08 


1.04 


1.13 


1.03 


1.13 


1.04 


1.14 






30 min 


1.01 


1.09 


1.01 


1.12 


1.00 


1.10 


1 00 


1.12 






60 min 


1.00 


1.07 


0.97 


1.15 


0.99 


1.10 


0.99 


1.12 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


1.03 


0.01 


1.02 i 0.02 


1.02 


0.02 


1.03 


0.03 






15 min 


1.07 


0.01 


1.08 


0.05 


1.08 


0.05 


1.09 


05 






30 mm 


1.05 


0.04 


1.06 


0.06 


1.05 


0.05 


1.06 


0.06 






60 min 


1.03 


0.04 


1.06 


09 


1.05 


0.06 


1.06 


0.07 




























186 



0.05% Ti02, TI02.XLS 





UV Light @ pH 4 






Raw Area 








Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor M 


21 


22 


21 


22 


21 


22 


21 


22 


21 


22 


min 


1643.32 


1975.62 


1097.35 


1 1 26.45 


501.67 


509.00 


208.42 


204.75 


327.1 


370.43 


5 min 


2535.57 


1370.45 


1654.29 


924.44 


793.58 


430.06 


317 14 


175.29 


313 07 


313 96 


15 min 


2825.57 


99667 


1899.02 


627 49 


903.89 


295.7 


368.85 


121.9 


305 08 


354.33 


30 min 


2103 24 


718.78 


1405.59 


453.68 


656.52 


218.60 


274.86 


87.78 


318 05 


339.04 


60 min 


1369.25 


709.19 


91 4.00 


45878 


435.61 


219.99 


173.16 


83 53 


293.1 


316.54 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


21 


22 


21 


22 


21 22 


21 22 


21 


22 


min 


1663.62 


1993.07 


1118.24 


1150.46 


514.32 


517.27 


214.29 


204.75 


33975 


377.11 


5 min 


2555.87 


1387.90 


1675.18 


948.45 


806.23 


438.33 


323.01 


175.29 


325.72 


320.64 


15 min 


2845.87 


1014.12 


1919.91 


651.50 


916.54 


303.97 


37472 


121.90 


317.73 


361.01 


30 min 


2123.54 


736.23 


1426.48 


477.69 


669.17 


226.87 


280.73 


87.78 


330.70 


345.72 


60 mm 


1389 55 


72664 


934 89 


482.79 


448.26 


228.26 


179.03 


83.53 


305.75 


323.22 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


21 


22 


21 


22 


21 


22 


21 22 


21 


22 


min 


490 


5.29 


3.29 


3.05 


1.51 


1.37 


0.63 


0.54 


0.1 


0.1 


5 min 


7.85 


433 


5.14 


2.96 


248 


1.37 


099 


0.55 


0.2 


0.1 


15 min 


8.96 


2.81 


6.04 


1.80 


2.88 


0.84 


1.18 


0.34 


0.3 


0.1 


30 min 


6.42 


2.13 


4.31 


1.38 


2.02 


066 


0.85 


0.25 


0.3 


0.2 


60 min 


4.54 


2.25 


306 


1.49 


1.47 


0.71 


0.59 


0.26 


0.3 


0.3 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor # 


21 


22 


21 22 


21 


22 


21 


22 


21 22 


min 


831 ppb 


902 ppb 


541 ppb 


497 ppb 


21 9 ppb 


1 93 ppb 


59 ppb 


43 ppb 


10.0 


10.0 


5 min 


683 ppb 


728 ppb 


438 ppb 


480 ppb 


196 ppb 


192 ppb 
97 ppb 


62 ppb 


43 ppb 


5.0 


10.0 


15 min 


522 ppb 


453 ppb 


346 ppb 


271 ppb 


156 ppb 


53 ppb 


5 ppb 


3.3 


10.0 


30 min 


369 ppb 


165 ppb 


242 ppb 


97 ppb 


104 ppb 


32 ppb 


33 ppb 


1 ppb 


3.3 


5.0 


60 min 


256 ppb 


117 ppb 


166 ppb 


72 ppb 


70 ppb 


24 ppb 


17 ppb 


1 ppb 


3.3 


3.3 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


21 


22 


21 


22 


21 


22 


21 


22 


■- 




mm 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


0.82 


0.81 


081 


0.97 


0.90 


1.00 


1.06 


1.02 






15 min 


0.63 


0.50 


64 


0.55 


0.71 


0.50 


0.90 


0.13 






30 min 


0.44 


0.18 


45 


0.20 


0.47 


0.16 


0.56 


0.02 






60 min 


0.31 


0.13 


0.31 


0.14 


0.32 


0.12 


0.29 


0.02 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avq 


SD 


Avq 


SD 


Avg 


SD 


Avq 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


081 


0.01 


0.89 


0.08 


0.95 


005 


1.04 


0.02 






15 min 


0.57 


0.06 


0.59 


0.05 


0.61 


0.10 


0.51 


0.39 






30 min 


0.31 


0.13 


0.32 


0.13 


0.32 


0.16 


0.29 


0.27 






60 min 


0.22 


0.09 


0.23 


08 


0.22 


0.10 


0.16 


0.13 





























187 



0.05% Ti02, TI02.XLS 



Reactor # 



min 



5 min 



15 min 



30 min 



60 min 



Reactor # 



min 



5 min 



15 min 
30 min 



60 min 



Reactor # 



min 



5 min 



15 min 



30 min 



60 min 



Reactor # 



min 



Benzene 



Raw Area 



Dark @ pH 4 



29 



1907.03 



1834.87 



1772.88 



1742.16 



1791.27 



30 



1767.5 



1834.88 



1570.57 



1375.2 



1704.33 



Toluene 



29 



1681.47 



1668.61 



1607.79 



1543.12 



1637.3 



30 



1547.71 



1611.21 



1377.59 



1065.97 



1519.13 



m&p-xylene 



29 



1131.47 



1097.55 



1073.81 



979.25 



1078.69 



30 



1048.55 



1072.41 



959.79 



657.69 



963.71 



Benzene 



29 



1924.45 



1852.29 



1790.30 



1759.58 



1808.69 



30 



1784.92 



1852.30 



1587.99 



1392.62 



1721.75 



Toluene 



Adjusted 



29 



o-xylene 



459.78 



456.92 



441.09 



407.88 



444.00 



29 



1707.66 



1694.80 



1633.98 



1569.31 



1663.49 



30 



1573.90 



1637.40 



1403.78 



1092.16 



1545.32 



m&p-xylene 



29 



1155.78 



1121.86 



1098.12 



1003.56 



1103.00 



Benzene 



29 



5.11 



5.13 



5.39 



4.44 



5.06 



30 



5.05 



5.01 



4.47 



3.78 



4.52 



Referenced 



30 



1072.86 



1096.72 



984.10 
682.00 



988.02 



30 



422.82 



443.04 



406.81 



308.63 



402.75 



29 



o-xylene 



472.54 



469.68 



453.85 



420.64 



456.76 



Toluene 



29 



4.54 



4.69 



4.92 



3.96 



4.65 



30 



4.45 



4.43 



3.95 



2.97 



4.06 



m&p-xylene 



29 



3.07 



3.11 



3.31 



2.53 



3.08 



Benzene 



29 



5 min 



870 ppb 



15 min 



873 ppb 



30 min 
60 min 



921 ppb 



748 ppb 



860 ppb 



30 



J55J^ppb 



853 ppb 



754 ppb 



629 ppb 



763 p pb 



Concentrations 



30 



3.04 



2.97 



2.77 



1.85 



2.59 



30 



435.58 



455.80 



419.57 



321.39 



Chlorobenzene 



29 



367.71 



35248 



323.20 



387.67 



348.92 



30 



344.67 



360.59 



346.52 



35955 



372.05 



Chlorobenzene 



29 



376.48 



361.25 



331 .97 



415.51 



29 



o-xylene 



1.26 



1.30 



1.37 



1.06 



1.28 



Toluene 



29 



766 p pb 



794 ppb 



836 ppb 



661 ppb 



787 ppb 



30 



751 ppb 



747 ppb 



660 ppb 



481 ppb 



679 p pb 



m&p-xylene 



29 



500 ppb 



507 ppb 



544 ppb 



403 p pb 



503 ppb 



30 



494 ppb 



482 p pb 



446 p pb 



280j3pb 



Benzene 



Reactor # 



29 



min 



1.00 



5 min 



1.00 



15 min 



1.06 



30 min 



0.86 



60 min 



0.99 



30 



1.00 



0.99 



0.88 



0.73 



0.89 



Norm alized Concentrations 



41 4 ppb 



30 



1.23 



1.23 



1.18 



0.87 



1.09 



o-xylene 



29 



172 ppb 



1 80 p pb 



1 92 ppb 



137 ppb 



1 76 p pb 



Toluene 



29 



1.00 



1.04 



1.09 



0.86 



1.03 



30 



1.00 



1.00 



0.88 



0.64 



0.90 



m&p-xylene 



29 



1.00 



1.01 



1.09 



0.81 



1.00 



Benzene 



Statistics 



30 



1.00 



0.98 



0.90 



0.57 



0.84 



30 



168 ppb 



1 68 pp b 



396.44 



357.69 



30 



353.44 



369.36 



355.29 



368.32 



38082 



Sample 



Dilution 



29 



0.1 



0.1 



0.1 



0.1 



0.1 



30 



0.1 



0.1 



0.1 



0.1 



0.1 



Dilution 



Factor 



29 



10 



30 



10 



1 58 ppb 



102 ppb 



142 ppb 



29 



o-xylene 



1.00 



1.05 



1.12 



0.80 



1.02 



min 

5 min 

15 min 

30 min 

60 mini 



Avg 



SD 



1.00 
1.00 
0.97 
0.80 
0.94 



0.00 
0.01 
0.09 
0.06 
0.05 



Avg 



Toluene 



30 



1.00 



1.00 



0.94 



0.61 



0.85 



SD 



m&p-xylene 



1.00 
1.02 
0.99 
0.75 
0.97 



JLQ0 
0.02 
0.11 
0.11 
0.06 



Avg 



SD 



1.00 
0.99 
0.99 
0.69 
0.92 



0.00 
0.02 
0.09 
0.12 
0.08 



Avg 



o-xylene 



SD 



1.00 
1.02 
1.03 
0.70 
0.94 



0.00 
0.02 
0.09 
0.09 
0.09 



10 



10 



10 



10 



10 



10 



10 



10 



188 



0.10% Ti02, TI02.XLS 





UV Light @ pH 7 




Raw Area 






Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


7 


8 


7 


8 


7 


8 


7 


8 


7 


8 


min 


1997.21 


1697.92 


1156.8 


932.8 


593.81 


450.32 


244 95 


185.52 


409.6 


336.98 


5 min 


1876.06 


1868.57 


1104.75 


1020.28 


544.55 


503.71 


221 .76 


205.76 


364.06 


342.17 


15 min 


1708.7 


1730.76 


950.57 


949.24 


493.06 


488.29 


200.84 


198.16 


368.58 


360.45 


30 min 


1363.74 


1529.45 


786.85 


848.59 


396.08 


427.53 


164.46 


170.51 


361.07 


370.85 


60 min 


1325.77 


1039.57 


726.26 


568.53 


367.49 


287.22 


149 57 


116.08 


360.44 


291.97 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor It 


7 


8 


7 


8 


7 


8 


7 8 


7 


8 


min 


2029.16 


1727.57 


1185.42 


974.54 


614.63 


481.11 


254.47 


199.41 


416.94 


344 20 


5 min 


1908.01 


1898.22 


1133.37 


1062.02 


565.37 


534.50 


231.28 


219.65 


371.40 


349.39 


15 min 


1740.65 


1760.41 


979.19 


990.98 


51 3.88 


519.08 


210.36 


212.05 


375 92 


367.67 


30 min 


1395.69 


1559.10 


815.47 


890.33 


416.90 


458.32 


173.98 


184.40 


368 41 


378.07 


60 mm 


1357.72 


1069.22 


754.88 


610.27 


388.31 


318.01 


159.09 


129.97 


367.78 


299.19 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


7 


8 


7 


8 


7 


8 


7 


8 


7 


8 


Omin 


4.87 


5.02 


2.84 


2.83 


1.47 


1.40 


0.61 


0.58 


0.1 


0.1 


5 mm 


5.14 


5.43 


3.05 


3 04 


1.52 


1.53 


0.62 


63 


0.1 


0.1 


15 min 


4.63 


4.79 


2.60 


2.70 


1.37 


1.41 


0.56 


0.58 


0.1 


0.1 


30 min 


3.79 


4.12 


2.21 


2.35 


1.13 


1.21 


0.47 


0.49 


0.1 


0.1 


60 min 


3.69 


3.57 


2.05 


2.04 


1.06 


1.06 


0.43 


0.43 


0.1 


0.1 




Concentrations 




Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor It 


7 


8 


7 


8 


7 


8 


7 


8 


7 


8 


Omin 


826 ppb 


854 ppb 


459 ppb 


457 ppb 


21 1 ppb 


198 ppb 


55 ppb 


49 ppb 


10 


10 


5 min 


875 ppb 


928 ppb 


497 ppb 


495 ppb 


220 ppb 


221 ppb 


57 ppb 


58 ppb 


10 


10 


15 min 


783 ppb 


81 2 ppb 


41 6 ppb 


433 ppb 


192 ppb 


200 ppb 


46 ppb 


49 ppb 


10 


10 


30 min 

60 mm 


631 ppb 


691 ppb 


345 ppb 


371 ppb 


149 ppb 


164 ppb 


30 ppb 


33 ppb 


10 


10 


61 3 ppb 


592 ppb 


31 6 ppb 


31 4 ppb 


136 ppb 


137 ppb 


23 ppb 


23 ppb 


10 


10 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor It 


7 


8 


7 


8 


7 


8 


7 


8 






Omin 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


1.06 


1.09 


1.08 


1.08 


1.04 


1.12 


1.04 


1.18 






15 min 


0.95 


0.95 


0.91 


0.95 


091 


1.01 


0.83 


0.99 






30 min 


0.76 


0.81 


0.75 


0.81 


0.71 


0.83 


054 


0.66 






60 min 


0.74 


0.69 


0.69 


0.69 


0.64 


0.69 


0.41 


0.47 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


1.07 


0.01 


1.08 


0.00 


1.08 


0.04 


1.11 


0.07 






15 min 


0.95 


0.00 


0.93 


0.02 


0.96 


005 


0.91 


0.08 






30 min 


0.79 


0.02 


0.78 


0.03 


0.77 


006 


0.60 


0.06 






60 min 


0.72 


0.02 


0.69 


0.00 


0.67 


0.03 


0.44 


0.03 



























189 



0.10% Ti02, TI02.XLS 



Reactor tt 



min 
5 min 



15 min 



30 min 
60 min 



Reactor # 



min 

5 min 

15 min 

30 min 

60 min 



Reactor It 



min 
5 min 



15 min 
30 min 
60 min 



Reactor t 



min 

5 min 

15 min 

30 min 

60 min 



Benzene 



Raw Area 



Dark @ pH 7 



Toluene 



15 



16 



15 



21 78.82 
2140.26 



1853.33 



1724.7 



1921.16 



2278.49 



1649.31 



1893.25 



1851.61 



2180.36 
2257.5 



1964.28 
1820.29 



1695.59 



1750.2 



16 



1479.23 



1537.86 



1459.82 



1511.15 



1408.06 



m&p-xylene 



15 



1227.72 



1189.07 



1329.57 



1260.78 



1240.53 



Benzene 



Toluene 



Adjus ted 



16 



1042.29 



1109.62 



1080.59 



1062.63 



1052.74 



15 



o-xylene 



486.67 



480.82 



534.1 



500.38 



505.92 



15 



16 



2200.88 
2162.32 
2300.55 



15 



1853.33 
1921.16 
1893.25 



1752.945 



1677.555 



2202.42 
2279.56 



1879.855 



1964.28 
1820.29 



1723.835 
1778.445 



16 



1479.23 



1537.86 



1459.82 



1511.15 



1408.06 



m&p-xylene 



15 



1256.605 



1217.955 



1358.455 



1289.665 



1269.415 



Benzene 



Referenced 



16 



1042.29 



1109.62 



1080.59 



1062.63 



1052.74 



16 



412.78 



444.5 



427.58 



433.86 



416.06 



Chlorobenzene 



15 
342.72 



341.64 



386.69 



351.19 



360.68 



15 



o-xylene 



500.235 



494.385 



547.665 



513.945 



51 9.485 



Toluene 



15 



16 



6.29 
6.20 



15 



5.10 
5.29 



5.01 



4.81 



Reactor tt 



min 

5 min 

15 min 

30 min 

60 min 



min 

5 min 

15 min 

30 min 

60 min 



5.84 
6.15 



5.35 



4.77 



5.56 



4.81 



6.20 



5.33 



4.84 



16 



4.07 



4.23 



4.12 



4.28 



4.12 



m&p-xylene 



15 



3.59 



3.49 



3.45 



3.60 



3.45 



Benzene 



Toluene 



Concentrations 



16 



2.87 



3.05 



3.05 



3.01 



3.08 



16 



412.78 



444.5 



427.58 



433.86 



41 6.06 



15 



o-xylene 



1.43 



1.42 



1.39 



1.43 



1.41 



15 



16 



15 



1 084 ppb 
1068 ppb 
1003 ppb 
1058 ppb 
1067 ppb 



867 ppb 
902 ppb 
91 3 ppb 



852 ppb 
816 ppb 



952 ppb 
909 ppb 



809 ppb 



81 6 ppb 



820 ppb 



16 



681 ppb 



71 1 ppb 



691 ppb 



71 9 ppb 



691 ppb 



m&p-xylene 



15 



595 ppb 



577 ppb 



569 ppb 



597 ppb 



570 ppb 



16 



463 ppb 



498 ppb 



497 ppb 



489 ppb 



Benzene 



Normalized Concentrations 



502 ppb 



16 



1.13 



1.22 



1.21 



1.23 



1.22 



15 



o-xylene 



16 



363.73 



363.25 



354.07 



353.25 



341 .67 



Chlorobenzene 



15 



349.74 



348.66 



393.71 



358.21 



367.7 



16 



363.73 



363.25 



354.07 



353.25 



341 .67 



Sample 



Dilution 



15 



0.1 



0.1 



0.1 



0.1 



0.1 



16 



0.1 



0.1 



0.1 



0.1 



0.1 



Dilution 



203 ppb 



201 ppb 



196 ppb 



204 ppb 



200 ppb 



Toluene 



15 



16 



15 



1.00 



1.00 



1.00 



0.98 



1.04 



0.96 



0.92 



1.05 



0.95 



0.98 
0.98 



1.10 
1.05 



0.96 



0.96 



16 



1.00 



1.04 



1.01 



1.06 



1.01 



m&p-xylene 



15 



1.00 



0.97 



0.96 



1.00 



0.96 



Benzene 



Statistics 



16 



1.00 



1.07 



1.07 



1.06 



1.08 



16 



150 ppb 



166 ppb 



163 ppb 



167 ppb 



165 ppb 



15 



o-xylene 



1.00 



0.99 



0.97 



1.00 



0.98 



Avg 



SD 



1.00 
1.01 
0.99 
1.04 
1.02 



0.00 
0.03 
0.06 
0.06 
0.03 



Avg 



Toluene 



SD 



1.00 
1.00 
0.98 
1.01 
0.99 



0.00 
0.04 
0.03 
0.05 
0.03 



m&p-xylene 



Avg 



SD 



1.00 
1.02 
1.01 
1.03 
1.02 ~ 



0.00 
0.05 
0.06 
0.03 
0.06 



16 



1.00 



1.11 



1.09 



1.11 



1.10 



Avg 



o-xylene 



SD 



1.00 
1.05 
1.03 
1.06 
1.04 



Factor 



15 



16 



10 



10 



10 



10 



10 



0.00 
0.06 
0.06 
0.05 
0.06 



10 



10 



10 



10 



10 



190 






0.10% Ti02, TI02.XLS 






Reactor It 



min 
5 min 



15 min 



30 min 
60 min 



Reactor # 



min 



5 min 



15 min 



30 min 
60 min 



Reactor # 



min 



5 min 
15 min 



30 min 
60 min 



Reactor # 



Benzene 



23 



24 



1651.67 



1682.29 



1553.54 



1727.82 



1403.71 1 



1575.74 



1322.98 



1305.94 



1063.27 



1080.04 



Raw Area 



UV Light @ pH 4 



Toluene 



23 



1100.09 



1066.94 



95892 



867.52 



675.39 



24 



1141.38 



1217.19 



1078.89 



894.61 



719.18 



m&p-xylene 



23 



522.23 



501.87 



448.75 



405.00 



317.17 



Benzene 



23 



24 



1669.12 



1699.74 



1570.99 



1745.27 



1421.16 



1593.19 



1340.43 
1080.72 



1323.39 
1097.49 



Toluene 



Adjusted 



24 



532.67 



563.75 



511.34 



421 .79 



345.59 



23 



o-xylene 



212.55 



210.36 



185.63 



168.66 



130.64 



23 



1124.10 



1090.95 



982.93 



891.53 



699.40 



24 



1165.39 



1241.20 



1 1 02.90 



918.62 



743.19 



23 



m&p-xylene 



530.50 



510.14 



457.02 



413.27 



325.44 



Benzene 



Referenced 



24 



540.94 



572.02 



519.61 



430.06 



353.86 



24 



215.54 



231 .70 



206.81 



175.05 



141.13 



23 



o-xylene 



212.55 



210.36 



185.63 



168.66 



130.64 



23 



Toluene 



24 



23 



4.97 



5.06 



3.35 



4.27 
3.93 



5.06 



2.97 



4.48 



2.72 



3.72 



3.83 



2.48 



3.01 



3.37 



1.95 



24 



3.47 



3.60 



3.10 



2.66 



2.28 



m&p-xylene 



23 



1.58 



1.39 



1.26 



1.15 



0.91 



Benzene 



Concentrations 



24 



1.61 



1.66 



1.46 



1.25 



1.09 



24 



215.54 



231 .70 



206.81 



175.05 



141.13 



Chlorobenzene 



23 



329.02 



360.94 



354.80 



353.36 



352.88 



24 



328.92 



338.23 



349.25 



338.56 



319.37 



Chlorobenzene 



23 



335.70 



367.62 



361 .48 



360.04 



23 



o-xylene 



0.63 



0.57 



0.51 



0.47 



0.36 



23 



Toluene 



24 



23 



min 



5 min 
15 min 

30 min 



845 ppb 



60 min 



71 8 ppb 
657 ppb 
61 9 ppb 



862 ppb 



861 ppb 

755 ppb 



551 ppb 
482 ppb 



489 ppb 



639 ppb 



437 ppb 



554 ppb 



393 ppb 



297 ppb 



24 



573 ppb 



596 pp b 



506 ppb 



426 ppb 



357 ppb 



m&p-xylene 



23 



231 ppb 



196 ppb 



173 ppb 



152 ppb 



108 ppb 



24 



236 ppb 



245 ppb 



2 09 ppb 



170 ppb 



Benzene 



Normalized Concentrations 



141 ppb 



24 



0.64 



0.67 



0.58 



0.51 



0.43 



23 



o-xylene 



59 ppb 



48 ppb 



37 ppb 



29 pp b 



10 ppb 



Reactor # 



23 



24 



Toluene 



23 



Omin 

5 min 

15 min 

30 min 

60 min 



min 

5 min 

15 min 

30 min 

60 min 



1.00 

0.85 

0.78 

0.73 " 

0.58" 



24 



1.00 
1.00 
0.88 
0.74 
0.64 



1.00 
0.87 
0.79 
0.71 
0.54 



Avg 



Benzene 



SD 



1.00 
0.92 
0.83 
0.74 
0.61 



JI00 
0.07 
0.05 
0.00 
0.03 



Avg 



Toluene 



1.00 
1.04 
0.88 
0.74 
JX62 _ 
Statistics 



m&p-xylene 
24 



24 



61 PPb 



66 ppb 



50 ppb 



36 ppb 



23 ppb 



359.56 



24 



335.60 



344.91 



355.93 



345.24 



326.05 



Sample 



Dilution 



23 



0.1 



0.1 



0.1 



0.1 



0.1 



24 



0.1 



0.1 



0.1 
0.1 



0.1 



Dilution 



Factor 



23 



10 



10 



10 



10 



10 



23 



23 



o-xylene 



24 



10 



10 



JO 

10 



10 



1.00 
0.85 
0.75 
0.66 
0.47" 



24 



1.00 
1.04 
0.88 
0.72 
0.60 



1.00 
0.81 
0.63 
0.49 
0.17 



1.00 
1.09 
0.82 
0.60 
0.37 



SD 



m&p-xylene 



1.00 
0.96 
0.84 
0.73 
0.58 



0.00 
0.08 
0.04 
0.02 
0.04 



Avg 



SD 



1.00 
0.94 
0.82 
0.69 
0.53 



0.00 
0.09 
0.07 
0.03 
0.06 



Avg 



o-xylene 



SD 



1.00 
0.95 
0.72 
0.55 
0.27 



0.00 
0.14 
0.09 
0.05 
0.10 



191 



0.10% Ti02, TI02.XLS 





Dark @ pH 4 






Raw Area 








Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor it 


31 


32 


31 


32 


31 


32 


31 


32 


31 


32 


min 


1827.06 


1830.94 


1617.42 


1602.38 


1067.34 


1062 94 


439.03 


432.33 


358.85 


346.21 


5 min 


1867.72 


1820.84 


1665.63 


1564.75 


1112.21 


1070.49 


447.98 


42653 


347.16 


344.88 


15 min 


1824.91 


1713.21 


1563.89 


1543.74 


1029.51 


1048.92 


427.31 


427.75 


348.18 


335.78 


30 min 


1606.19 


1786.41 


1413.13 


1598.49 


873.77 


1065.27 


383.24 


438.77 


351.52 


401.31 


60 min 


1711.94 


1778.02 


1519.03 


1574.86 


96938 


1031.9 


41 1 .56 


428.24 


338.77 


360.21 




Adjusted 










Benzene 


Toluene 


m&p-xylene 


o-xylene 


Chlorobenzene 


Reactor # 


31 


32 


31 


32 


31 


32 


31 


32 


31 


32 


min 


1848.54 


1852.42 


1655.51 


1640.47 


1095.15 


1090.75 


452.05 


445.35 


366.08 


353.44 


5 min 


1889.20 


1842.32 


1703.72 


1602.84 


1 1 40.02 


1098.30 


461.00 


439.55 


354.39 


352.11 


15 min 


1846.39 


1734.69 


1601.98 


1581.83 


1057.32 


1076.73 


440.33 


440.77 


355.41 


343.01 


30 min 


1627.67 


1807.89 


1451.22 


1636.58 


901.58 


1093.08 


396.26 


451.79 


358.75 


408.54 


60 min 


1733.42 


1799.50 


1557.12 


1612.95 


997.19 


1059.71 


424.58 


441.26 


346.00 


367.44 




Referenced 




Sample 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Dilution 


Reactor # 


31 


32 


31 


32 


31 


32 


31 


32 


31 


32 


min 


5.05 


5.24 


4.52 


4.64 


2.99 


3.09 


1.23 


1.26 


0.1 


0.1 


5 min 


5.33 


5.23 


4.81 


455 


3.22 


3.12 


1.30 


1.25 


0.1 


0.1 


15 min 


5.20 


5.06 


4.51 


4.61 


2.97 


3.14 


1.24 


1.28 


0.1 


0.1 


30 min 


4.54 


4.43 


4.05 


4.01 


2.51 


2.68 


1.10 


1.11 


0.1 


0.1 


60 min 


501 


490 


4.50 


4.39 


2.88 


2.88 


1.23 


1.20 


0.1 


0.1 






Concentrations 






Dilution 




Benzene 


Toluene 


m&p-xylene 


o-xylene 


Factor 


Reactor # 


31 


32 


31 


32 


31 


32 


31 


32 


31 


32 


min 


859 ppb 


894 ppb 


764 ppb 


785 ppb 


486 ppb 


503 ppb 


168 ppb 


173 ppb 


10 


10 


5 min 


91 ppb 


892 ppb 


81 5 ppb 


769 ppb 


527 ppb 


509 ppb 


180 ppb 


170 ppb 


10 


10 


15 min 


885 ppb 


860 ppb 


761 ppb 


780 ppb 


483 ppb 


51 3 ppb 


169 ppb 


177 ppb 


10 


10 


30 min 


766 ppb 


746 ppb 


677 ppb 


670 ppb 


400 ppb 


429 ppb 


144 ppb 


145 ppb 


10 


10 


60 min 


852 ppb 


831 ppb 


760 ppb 


740 ppb 


466 ppb 


467 ppb 


167 ppb 


162 ppb 


10 


10 




Normalized Concentrations 










Benzene 


Toluene 


m&p-xylene 


o-xylene 






Reactor # 


31 


32 


31 


32 


31 


32 


31 32 






min 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 


1.00 






5 min 


1.06 


1.00 


1.07 


0.98 


1.08 


1.01 


1.07 


99 






15 min 


1.03 


0.96 


1.00 


0.99 


0.99 


1.02 


1.00 


1.03 






30 min 


0.89 


0.83 


089 


0.85 


0.82 


0.85 


0.86 


0.84 






60 min 


0.99 


0.93 


0.99 


0.94 


0.96 


0.93 


0.99 


0.94 








Statistics 










Benzene 


Toluene 


m&p-xylene 


o-xylene 








Avg 


SD 


Avg 


SD 


Avg 


SD 


Avg 


SD 






min 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 


1.00 


0.00 






5 min 


1.03 


0.03 


1.02 


0.04 


1.05 


0.04 


1.03 


0.04 






15 min 


1.00 


0.03 


0.99 


0.00 


1.01 


0.01 


1.02 


0.01 






30 mm 


0.86 


0.03 


0.87 


0.02 


0.84 


0.02 


0.85 


0.01 






60 min 


096 


0.03 


0.97 


0.03 


0.94 


0.02 


0.96 


0.03 

















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T Adj Area 
436.97 
474.49 
420.43 

Toluene Ref 
1.71 
1.75 
1.59 

Toluene Ref 
435 3 ppb 
448.6 ppb 
393.3 ppb 

Toluene Ref 
1.00 
1.03 

0.90 

Avg 
cfuA. x 10*3 


1 .0 mg/L) 

Tol Area 

445.16 

482.68 

428.62 

Benzene Ref 
2.41 
2.36 
2.18 

Benzene Ref 
949.3 ppb 
925.1 ppb 
846.0 ppb 

Benzene Ref 
1.00 
0.97 
0.89 

C 
%Dest 


3( 

BAdjArea 

613.90 

636.88 

578.17 

Adj Area 
254.89 
270.39 
265.00 

Toluene 
354.69 
402.78 
333.49 

Toluene 
1.00 
1.14 
0.94 

8 
%SD 


Benz Area 
621.55 
644.53 
585.82 

Raw Area 

254.89 

270.39 

265 

Benzene 
863.16 
903.75 
800.04 

Benzene 
1.00 
1.05 
0.93 

A 
SD 


0) 

T Adj Area 
513.26 
445.59 
407.86 

Toluene Ref 
2.06 
1.48 
1.46 

Toluene Ref 

549.4 ppb 

357.1 ppb 

351.0 ppb 

> 

Toluene Ref 

1.00 

0.65 

0.64 

Avg 
cfu/L x 10*3 


Sunlight (pH=' 
D.1 mg/L) 
Tol Area 
521.45 
453.78 
416.05 
obenzene 
Benzene Ref 
2.72 
1.99 
2.02 
entrations 
Benzene Ref 
1091 .4 ppb 

759.5 ppb 

771.6 ppb 
Concentration! 

Benzene Ref 
1.00 
0.70 
0.71 
E. coli 
C 

%Dest 


2( 
BAdjArea 
677.25 
601.20 
564.77 
Chloi 
Adj Area 
248.93 
301.83 
279.82 
Cone 
Toluene 
452.47 
365.74 
317.38 
Normalized 
Toluene 
1.00 
0.81 
0.70 

e 

%SD 


Benz Area 
684.9 
608.85 
572.42 

Raw Area 
248.93 
301.83 
279.82 

Benzene 
975.07 
840.72 
776.36 

Benzene 
1.00 
0.86 
0.80 

A 
SD 


T Adj Area 
672.66 
457.27 
397.01 

Toluene Ref 
2.73 
1.82 
1.35 

Toluene Ref 

770 ppb 

471.6 ppb 

314.1 ppb 

Toluene Ref 
1.00 
0.61 
0.41 

Avg 
cfu/L x 10*3 


(control) 

Tol Area 

680.85 

465.46 

405.20 

Benzene Ref 
3.00 
2.54 
1.82 

Benzene Ref 

1218 ppb 

1009.4 ppb 

679.6 ppb 

Benzene Ref 
1.00 
0.83 
0.56 

c 

%Dest 


1 

BAdjArea 

737.97 

636.62 

536.12 

Adj Area 
246.02 
250.58 
295.17 

Toluene 
656.78 
380.71 
303.48 

Toluene 
1.00 
0.58 
0.46 

e 

%SD 


Benz Area 
745.62 
644.27 
543.77 

Raw Area 
246.02 
250.58 
295.17 

Benzene 
1082.34 
903.29 
725.75 

Benzene 

1.00 

0.83 

0.67 

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222 



T Adj Area 
547.79 
409.36 
359.85 

Toluene Ref 
1.79 
1.48 
1.34 

Toluene Ref 
461.5 ppb 
357.5 ppb 
31 1.9 ppb 

Toluene Ref 
1.00 
077 
0.68 

Avg 
80.0 
18.0 

1.0 

1.0 

1.3 

0.5 

0.0 
cfuA x 10 3 
800.0 
180.0 
10.0 
10.0 
13.3 

5.0 

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1.0 mg/L) 

Tol Area 

556.45 

418.02 

368.51 

Benzene Ref 
2.29 
2.02 
1.91 

Benzene Ref 
897 5 ppb 
771.1 ppb 
722.4 ppb 

Benzene Ref 
1.00 
0.86 

080 

C 

79 

18 

4 

%Dest 
0.0% 
77.5% 
98.8% 
98.8% 
98.3% 
99.4% 
100.0% 


8( 

BAdj Area 

700.68 

558.93 

513.55 

Adj Area 
305.33 
277.08 
268.83 

Toluene 
496.74 
319.31 
255.85 

Toluene 
1.00 
0.64 
0.52 

B 
94 

20 
1 






%SD 
13.8% 
9.1% 
0.0% 
0.0% 
141.4% 
100.0% 
0.0% 


Benz Area 
721.46 
579.71 
534.33 

Raw Area 
305.33 
277.08 
268.83 

Benzene 
1016.46 
766.05 
685.88 

Benzene 
1.00 
0.75 
0.67 

A 

67 

16 

1 

1 

SD 

11.0 

1.6 

0.0 

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0.5 

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= 7) 

TAdjArea 
544.97 
406.76 
342.68 

Toluene Ref 
1.82 
1.42 
1.12 

Toluene Ref 
470.0 ppb 
337.5 ppb 
241.0 ppb 

Toluene Ref 
1.00 
0.72 
0.51 

Avq 

805 

64.0 

42.3 

12.5 

0.3 

0.0 

0.0 
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805.0 
640.0 
423.3 
125.0 

3.3 

0.0 

0.0 


SUNLIGHT (pH 
3.1 mg/L) 
Tol Area 
553.63 
415.42 
351.34 
obenzene 
Benzene Ref 
2.35 
1.95 
1.55 
entrations 
Benzene Ref 
921.2 ppb 
741.6 ppb 
557.8 ppb 
Concentration: 
Benzene Ref 
1.00 
0.81 
0.61 
'. coli 

C 

57 

41 

15 






"ADest 
0.0% 
20.5% 
47.4% 
84.5% 
99.6% 
100.0% 
100.0% 


7 
BAdjArea 
702.68 
560.73 
472.82 
Chloi 
Adj Area 
299.42 
287.20 
305.26 
Cone 
Toluene 
493.12 
315.98 
233.85 
Normalized 
Toluene 
1.00 
0.64 
0.47 

£ 
B 
82 
81 
38 

1 




%SD 
1.9% 
18.9% 
9.9% 
20.0% 
141.4% 
0.0% 
0.0% 


Benz Area 
723.46 
581.51 
493.6 

Raw Area 
299.42 
287.2 
305.26 

Benzene 
1019.99 
769.23 
613.92 

Benzene 
1.00 
0.75 
0.60 

A 

79 

54 

48 

10 






SD 
1.5 
12.1 
4.2 
2.5 
0.5 
0.0 
0.0 


TAdjArea 
498.88 
428.57 
358.22 

Toluene Ref 
1.58 
1.52 
1.26 

Toluene Ref 
390.5 ppb 
371 .3 ppb 
286.1 ppb 

Toluene Ref 
1.00 
0.95 
0.73 

Avq 

78.7 

53.7 

54.0 

42.0 

1.0 

0.0 

0.0 
cfuA x 10 ' 
786.7 
536.7 
540.0 
420.0 

10.0 

0.0 

0.0 


(control) 

Tol Area 

507.54 

437.23 

366.88 

Benzene Ref 
2.01 
2.08 
1.82 

Benzene Ref 
768.9 ppb 
799.8 ppb 
679.5 ppb 

Benzene Ref 
1.00 
1.04 
0.88 

C 

96 

53 

66 

26 






"ADest 
0.0% 
31.8% 
31.4% 
46.6% 
98.7% 
100.0% 
100.0% 


6 

BAdj Area 

636.24 

586.78 

516.39 

Adj Area 
316.16 
282.07 
284.36 

Toluene 
434.05 
343.93 
253.76 

Toluene 
1.00 
0.79 
0.58 

B 

79 

71 

41 

45 





°ASD 
18.2% 
25.9% 
18.9% 
28.6% 
141.4% 
0.0% 
0.0% 


Benz Area 
657.02 
607.56 
537.17 

Raw Area 
316.16 
282.07 
284.36 

Benzene 
902.62 
815.25 
690.89 

Benzene 
1.00 
0.90 
0.77 

A 

61 

37 

55 

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14.3 
13.9 
10.2 
12.0 

1.4 
0.0 
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(minutes) 

60 
240 



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240 



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240 



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TAdi Area 
515.62 
405.61 
321.93 

Toluene Ref 
1.23 
0.89 
0.75 

Toluene Ref 
154.2 ppb 
93.6 ppb 
66.9 ppb 

Toluene Ref 
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0.61 
0.43 

Avg 
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412.80 

329.12 

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1.44 
1.27 

Benzene Ref 
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289.9 ppb 
245.1 ppb 

Benzene Ref 
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0.70 
0.59 

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%Dest 

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BAdjArea 

802.59 

653.14 

545.31 

Adj Area 
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453.64 
430.14 

Toluene 
141.79 
93.73 
57.17 

Toluene 
1.00 

0.66 
0.40 

B 
67 






%SD 
16.6% 
57.6% 
0.0% 

0.0% 

0.0% 

0.0% 


Benz Area 
810.42 
660.97 
553.14 

Raw Area 
429.2 
462.25 
438.75 

Benzene 
400.18 
307.06 
239.87 

Benzene 
1.00 
0.77 
0.60 

A 
59 

5 








SD 
11.8 
2.5 
0.0 
0.0 

0.0 
0.0 


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SUNLIGHT (pH 

(0.1 mg/L) 
Tol Area 
504.44 
450.67 
349.59 
robenzene 
Benzene Ref 
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1.72 
1.31 
'.entrations 
Benzene Ref 
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363.0 ppb 

257.1 ppb 

1 Concentrator 

Benzene Ref 

1.00 

0.95 

0.67 

E, coll 

C 







'ADest 

0.0% 

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94.9% 

100.0% 

98.3% 

100.0% 

100.0% 


7 
B Adj Area 
781.75 
727.42 
570.38 
Chlo 
Adj Area 
434.86 
422.82 
434.04 
Com 
Toluene 
133.76 
110.27 
66.11 
Normalizec 
Toluene 
1.00 
0.82 
0.49 

B 

37 

21 

3 



2 




%SD 
5.1% 
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141.4% 
0.0% 
0.0% 


Benz Area 
789.58 
735.25 
578.21 

Raw Area 
443.47 
431.43 
442.65 

Benzene 
387.20 
353.34 
255.49 

Benzene 
1.00 
0.91 
0.66 

A 
41 

1 






SD 
2.0 
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1.0 
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0.0 


TAdj Area 
522.72 
356.44 
379.13 

Toluene Ref 
1.16 
0.97 
0.79 

Toluene Ref 
141.3 ppb 
107.0 ppb 
74.9 ppb 

Toluene Ref 
1.00 
0.76 
0.53 

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49.0 

44.5 

11.0 

4.0 

0.5 

0.0 

0.0 

cfuA. x 10 3 

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445.0 

110.0 

40.0 

5.0 

0.0 

0.0 


(control) 

Tol Area 

529.91 

363.63 

386.32 

Benzene Ref 
1.77 
1.63 
1.27 

Benzene Ref 
377.0 ppb 

340.4 ppb 

245.5 ppb 

Benzene Ref 
1.00 
0.90 
0.65 

C 

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"ADest 

0.0% 

9.2% 

77.6% 

91.8% 

99.0% 

100.0% 

100.0% 


6 

BAdjArea 

802.84 

601.72 

607.59 

Adj Area 
452.49 
368.32 
478.66 

Toluene 
144.89 
72.24 
82.16 

Toluene 
1.00 
0.50 
0.57 

B 

45 
11 
5 




%SD 
0.0% 
1.1% 
0.0% 
35.4% 
100.0% 
0.0% 
0.0% 


3-May-98 

Benz Area 
810.67 
609.55 
615.42 

Raw Area 
461.1 
376.93 
487.27 

Benzene 
400.34 
275.02 
278.68 

Benzene 
1.00 
0.69 
0.70 

A 

49 

44 

5 






SD 
0.0 
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0.0 
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0.0 
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X 



APPENDIX B 
LIGHT MEASUREMENT 

The light available for experiments were measured using an Eppley 
TUVR Model Ultraviolet Radiometer for UV light, and Eppley PSP 
Pyranometer for total sunlight. Both instruments were factory calibrated 
for use outdoors. During outdoor experiments, the measurements were 
taken continuously for the duration of the experiments. Charts for these 
experiments are shown below. 

For the experiments conducted in the chamber, the measurements 
were taken at the same distance from the lamps as the reactors were 
located. The radiometer gave a stable reading over a period of several 
hours. The measurement taken for the UV lamps in the chamber was 
adjusted to account for the difference in the spectrum from sunlight and 
the UV lamps. 

The recorder was jammed for about the last half hour of the 
Combination Experiment in experimental set three, so that the values for 
that experiment are estimated based on measurements before the recorder 
jammed and the maximum and minimum values while it was jammed. 



260 



261 








Solar Insolation for Methylene Blue Experiment 
Set#1, pH =7 




Qon 






800 

700 






^^^^—^^ 




600 


^^^^^ 






- E 500 
^ 400 


^ 






300 








200 


Average = 684.95 W/m 2 






100 - 








- 








( 


) 30 60 90 120 150 180 210 

Time (minutes) 


240 





Solar Insolation for Methylene Blue Experiment 

Set #1, pH 10 




900 






800 








700 








600 








~ E 500 








1 400 


- 






300 








200 
100 


Average = 671.38 W/m 2 






J 








c 


I I I I I \ 1 

• 30 60 90 120 150 180 210 

Time (minutes) 


240 



262 



Solar Insolation for Methylene Blue Experiment 
Set #2, pH = 7 



1000 
800 
600 


w 


\y- r V r y^ 


pVT 


% 


n hh 


400 

200 




Average = 665.16 W/m 

' 1 1 1 — 


I 

2 

1 


"Will 

H 1 1 



30 60 



90 120 150 
Time (minutes) 



180 210 240 



Solar Insolation for Methylene Blue Experiment 
Set #2, pH =10 




Average = 542.36 W/m 2 



— i 1 1 1 1 1 1 

30 60 90 120 150 180 210 240 

Time (minutes) 















263 





Solar Insolation for Methylene Blue Experiment 
Set #3, pH = 7 




1 nnn 






900 








800 


-^. ' 






700 
600 


. 






I 500 
400 


" 






300 








200 


Average = 891.53 W/m 2 






100 ■ 








n 








( 


I I I I I I I 

) 30 60 90 120 150 180 210 240 




Time (minutes) 





Solar Insolation for Methylene Blue Experiment 
Set #3, pH = 10 



1200 
1000 
800 
600 
400 
200 



JHM 



A 



y 



A 



v 



Average = 696.12 W/m 2 



Si 




H 1 H 



30 60 90 120 150 180 210 

Time (minutes) 



240 



264 





Solar Insolation for Rose Bengal Experiment 
Set #1 , pH 7 




900 






800 








700 








600 








" E 500 - 








> 400 








300 - 


~ 






200 


Average = 746.05 W/m 2 






100 


- 






n 








c 


I I I I — f 

I 30 60 90 120 150 180 210 

Time (minutes) 


240 



900 

800 4 

700 

600 

"fc 500 

§ 400 

300 

200 

100 






Solar Insolation for Rose Bengal Experiment 
Set#1, pH 10 



Average = 715.23 W/m 2 



+ 



30 60 90 120 150 
Time (minutes) 



180 210 240 



265 





Solar Insolation for Rose Bengal Experiment 
Set #2, pH =7 




1 nnn 






900 


~^M 








800 


^ J ~-^^ r ^ r 








700 


* 








600 










| 500 
400 


- 














300 


r | 






200 
100 


Average = 856.32 W/m 2 






n 








( 


I I I I I I I 

) 30 60 90 120 150 180 210 

Time (minutes) 


240 



Solar Insolation for Rose Bengal 
Set #2, pH =10 




60 



90 120 150 

Time (minutes) 



180 210 240 



266 



500 
400 
300 
200 
100 




Solar Insolation for Rose Bengal Experiment 
Set #3, pH =7 




Average = 841.34 W/m 2 



30 60 90 120 150 180 210 240 

Time (minutes) 



Solar Insolation for Rose Bengal Experiment 
Set #3, pH = 10 



1200 
1000 




800 




600 




400 




200 




i 






Average = 749.34 W/m 2 



30 60 



90 120 150 

Time (minutes) 



180 210 240 



267 



Solar Insolation for Combination Experiment 
Set #1 




300 

200 

100 





Average T oT = 779.68 W/m 2 
Averageuv = 38.95 W/m 2 



30 60 90 

Time (minutes) 



10 



120 



-Total 
■-UV 



920 
900 
880 



§ 860 -, r 



Solar Insolation for Combination Experiment 
Set #2 



60 
50 
40 




S 840 - 
o 



Average TO T= 852.58 W/m 2 
Averageuv= 39.98 W/m 2 



c 
< 

h 30 5 

3 

20 N 



10 



30 60 90 

Time (minutes) 



120 



■Total 
■UV 















268 



600 



Solar Insolation for Combination Experiment 
Set #3 

60 



200 

100 





A/ 



^ v /V-*-~~V ' 



Average T0 T= 432.79 W/m 2 
Average uv = 24.87 W/m 2 




r 



30 60 90 

Time (minutes) 



c 
< 

30 5 

3 
20 

10 





Total 

UV 



120 






BIOGRAPHICAL SKETCH 

Adrienne Teresa Cooper was born in Baton Rouge, Louisiana, on 
August 21, 1962. She received her undergraduate degree in chemical 
engineering from the University of Tennessee in June 1984. Following 
graduation she joined E. I. DuPont de Nemours and Company, Inc., as an 
engineer in the research and development division of the Chemicals & 
Pigments Department. She remained with DuPont until 1992 in various 
assignments as a chemical engineer, business analyst, and diversity 
education consultant. 

From 1990 through 1993 she served on the Alumni Executive Board of 
the National Society of Black Engineers. She is also a member of the 
American Solar Energy Society, the International Society of African 
Scientists and the International Solar Energy Society. She is certified as an 
Engineer Intern in the state of Florida. 

After leaving DuPont and following a brief stint in West Africa, she 
enrolled in the doctoral program at the University of Florida Department of 
Environmental Engineering Sciences. During her tenure in Gainesville, 
she worked as en environmental engineer for the Alachua County 
Department of Environmental Protection and as an instructor in college 
prep math at Santa Fe Community College. 



269 



I certify that I have read this study and that in my opinion it 
conforms to acceptable standards of scholarly presentation and is fully 
adequate, in scope and quality, as a dissertation for the degree of Doctor of 
Philosophy. 




'/?->*£? 




Thomas L. Crismarf, Chairman 
Professor of Environmental 
Engineering Sciences 



I certify that I have read this study and that in my opinion it 
conforms to acceptable standards of scholarly presentation and is fully 
adequate, in scope and quality, as a dissertation for the degree of Doctor of 
Philosophy. 

D. Yogi Goswami, Cochairman 
Professor of Mechanical 
Engineering 

I certify that I have read this study and that in my opinion it 
conforms to acceptable standards of scholarly presentation and is fully 
adequate, in scope and quality, as a dissertation for the degree of Doctor of 
Philosophy. 




Michael Annable 
Associate Professor of 

Environmental Engineering 

Sciences 



I certify that I have read this study and that in my opinion it 
conforms to acceptable standards of scholarly presentation and is fully 
adequate, in scope and quality, as a dissertation for the degree of Doctor of 
Philosophy. 



Seymour S. Block 
Professor Emeritus of 
Chemical Engineering 



I certify that I have read this study and that in my opinion it 
conforms to acceptable standards of scholarly presentation and is fully 
adequate, in scope and quality, as a dissertation for the degree of Doctor of 
Philosophy. 



3^4> 



Paul A. Chadik 
Assistant Professor of 

Environmental Engineering 

Sciences 



I certify that I have read this study and that in my opinion it 
conforms to acceptable standards of scholarly presentation and is fully 
adequate, in scope and quality, as a dissertation for the degree of Doctor of 
Philosophy. 



t£S 




Jonathan F. K. Earle 
Associate Professor of 
Agricultural 
and Biological Engineering 



This dissertation was submitted to the Graduate Faculty of the 
Department of Environmental Engineering Sciences in the College of 
Engineering and to the Graduate School and was accepted as partial 
fulfillment of the requirements for the degree of Doctor of Philosophy. 

August, 1998 



Winfred M. Phillips 

Dean, College of Engineering 



Dean, Graduate School 



LD 

1780 

1991 

,C776 






UNIVERSITY OF FLORIDA 



3 1262 08554 8450